Ellipticine derivative and production process thereof

ABSTRACT

An ellipticine derivative having the structure: ##STR1## as well as process for the preparation of such ellipticine derivatives. The ellipticine derivatives have antineoplastic or antitumor activity.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel ellipticine derivative having astrong antineoplastic or antitumor activity and, also, relates to aproduction process thereof.

2. Description of the Related Art

Pyridocarbazole alkaloids such as ellipticine, i.e., 5,11-dimethyl-6H-pryrido [4,3-b] carbazole (i.e., R=H in the followinggeneral formula (A)), and 9 -methoxyellipticine (i.e., R=OCH₃ in thefollowing general formula (A)) are known as alkaloids contained in, forexample, Aspidospermina and Ochrosia leaves. ##STR2##

Recently, it was reported in J. Rouess'e et. al, Bull. Cancer (Paris),68, 437-441 (1981) that 2-methyl-9-hydroxyelliptiscinium acetate(Celiptium) having the general formula (B): ##STR3## is effectiveagainst mammary cancer. It was also reported, in R.W. Guthrie et. al, J.Medicinal Chemistry, 18 (7), 755-760 (1975), that elipticine and9-methoxyellipticine are effective against the tumor of animals used forexperiments, mouse lymphoid leukemia L-1210 and Sarcoma 180 (solid) and,in Japanese Examined Patent Publication (Kokoku) No. 58-35196 andBritish Pat. No. 1436080, that the activity of 9-hydroxyellipticineagainst mouse lymphoid leukemia L-1210 is higher, by more than 100 to1000 fold, than that of 9-methoxyellipticine.

As mentioned above, compounds having a pyridocarbazole skeleton areuseful because they have an antineoplastic or antitumor activity.Various studies or research to synthesize those compounds have beenreported in, for example, L.K. Dalton et. al., Aust. J. Chem., 20,2715-2727 (1967); A.H. Jackson et. al., J. Chem. Soc. Perkin I,1698-1704 (1977); J.Y. Lallemand et. al, Tetrahedron Letters, No. 15,1261-1264 (1978); and European Patent Specification No. 9445.Furthermore, it is disclosed in U.S. Pat. No. 4,434,290 that compoundshaving certain substituents introduced into the pyridocarbazole skeletonhave an activity against mouse lymphoid leukemia L-1210.

However, ellipticine, 9-methoxyellipticine, and 9-hydroxyellipticinehave not been clinically used yet as an antineoplastic or antitumoragent. This is because, among other reasons, the water-solubilities ofthese compounds are very poor. Although Japanese Unexamined PatentPublication (Kokai) No. 58-222087 proposes the oxidation of2-alkyl-9-hydroxyellipticinium salts to introduce amino acids,oligopeptides, nucleotides, or nucleosides into the 10-position of theskeleton. However, these compounds do not provide desirablelife-prolongation effects against mouse lymphoid leukemia L-1210.

SUMMARY OF THE INVENTION

Accordingly, the objects of the present invention are to improve theabove-mentioned state of the prior art and to provide novel ellipticinederivatives having a remarkable antineoplastic or antitumor activity.

Other objects and advantages of the present invention will be apparentfrom the following description.

In accordance with the present invention, there is provided anellipticine derivative having the general formula (I): ##STR4## whereinR¹ represents a hydrogen atom, a hydroxyl group, an alkoxyl group having1 to 4 carbon atoms, or an acyloxy group having 2 to 7 carbon atoms;

R² represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, analdohexuronic acid residue, an acylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated deoxyaldose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atomsan acylated N-acylamino aldose residue having, an amino groupsubstituted with an acyl group with 2 to 4 carbon atoms and having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated aldohexuronic amide residue having,subsituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated aldohexuronic acid residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated aldohexuronic acid ester residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an arylalkylated aldose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated deoxyaldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylatedN-acylaminoaldose residue having an amino group with an acyl group with2 to 4 carbon atoms and having, substituted for the hydrogen of thehydroxyl group of the sugar, an arylalkyl group with 7 to 8 carbon atomsan arylalkylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic acid residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, an arylalkylatedaldohexuronic acid ester residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; and

R³ represents a hydrogen atom, a linear, branched, cyclic, orcyclic-linear alkyl group having 1 to 5 carbon atoms;

X.sup.⊖ represents a pharmaceutically acceptable inorganic or organicacid anion; and

The bond represented by N.sup.⊕ --R² in the general formula (I)represents a glycoside bond between a nitrogen atom in the 2-position ofthe ellipticine and a carbon atom in the 1-position of the sugar.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The present inventors have noticed the antineoplastic or antitumoractivities of ellipticine in the course of their study to developvarious useful derivative having pharmaceutical activities derived fromnaturally occurring skeletones. It has been intended to improve the verypoor water-solubility of the skeleton of the ellipticine. It is known inthe art that alkyl groups, hydroxyalkyl groups, aminoalkyl groups andthe like are introduced into the nitrogen atom in the 2-position ofellipticine as shown in U.S. Pat. No. 4,310,667. It has been found that,when sugar is introduced into the nitrogen atom in the 2-position ofellipticine, to improve the water-solubility of ellipticine, theresultant ellipticine derivatives having the above-mentioned generalformula (I) are useful compounds having the desired water-solubility andremarkably strong antineoplastic or antitumor activity.

The introduction of sugar into the nitrogen atom in the 2-position ofellipticine can be readily carried out in the same manner as in thewell-known reaction used in the synthesis of nicotinic amide nucleotidewherein sugar makes a covalent bond with the nitrogen atom of thepyridine ring to form a quaternary salt, as disclosed in, for example,L.J. Haynes et, al., J. Chem, Soc., 303-308 (1950) and L.J. Haynes et.al. J. Chem. Soc., 3727-3732 (1957). Furthermore, it is expected, asdisclosed in S. C. Jain et. al., J. Mol. Biol., 135, 813-840 (1979),that the introduction of a substituent having an appropriate size and ahydrophilic property into the nitrogen atom in the 2-position ofellipticine further increases the affinity thereof with the base ofnucleic acid.

The ellipticine derivatives having the general formula (I) can bereadily produced from ellipticine derivatives having the followinggeneral formula (II) according to the present invention. ##STR5##wherein R¹ and R³ are the same as defined above. Of the ellipticinederivatives having the general formula (II), ellipticine (R¹ =H, R³ =H),and 9-methoxyellipticine (R¹ =OCH₃, R³ =H) are naturally occuringalkaloids as mentioned above. These natural substances can be used as astarting material in the present invention. The ellipticine derivatives(II) can be prepared from pyridocarbazoles as described in, for example,L.K. Dalton et. al., Aust. J. Chem., 20, 2715-2727 (1967). Furthermore,the ellipticine derivatives (II) having an alkyl group with 1 to 5carbon atoms as R³ of the general formula (II) can be prepared by, forexample, treating the above-mentioned ellipticine derivatives having ahydrogen atom as R³ of the general formula (II) with a base such assodium hydride, potassium hydride, potassium t-butoxide, ortriphenylmethyl sodium in an organic solvent such as amido or other typesolvents, preferably dimethylformamide to form the alkali metal salts,followed by the addition of the corresponding alkyl halides such asmethyl iodide, ethyl iodide, propyl iodide, isopropyl iodide, butyliodide, sec-butyl iodide, isobutyl iodide, pentyl iodide,cyclopropylmethyl iodide, cyclobutylmethyl iodide, cyclopropylethyliodide, methyl bromide, ethyl bromide, propyl bromide, isopropylbromide, butyl bromide, sec-butyl bromide, isobutyl bromide, pentylbromide, cyclopropylmethyl bromide, cyclobutylmethyl bromide, andcyclopropylethyl bromide.

According to the present invention, the abovementioned ellipticinederivatives (II) are reacted with aldose derivatives having thefollowing general formula (III) upon heating (e.g., 80° C. to 130° C.)in the presence or absence of an acid captured reagent in an organicsolvent.

    R.sup.4 --Y                                                (III)

wherein R⁴ represents an acylated aldose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated deoxyaldose residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an alkylacyl group with 2 to 4carbon atoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedN-acylaminoaldose residue having an amino group substituted with an acylgroup with 2 to 4 carbon atoms and having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an alkylacyl group with 2 to 4carbon atoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedaldohexuronic amide residue having, substituted for the hydrogen atom ofthe hydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbonatoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedaldohexuronic acid ester residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an alkylacyl group with 2 to 4carbon atoms or an arylacyl group with 7 to 9 carbon atoms, anarylalkylated aldose residue having, substituted for the hydrogen atomof the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms, an arylalkylated deoxyaldose residue having, substitutedfor the hydrogen atom of the hydroxyl group of the sugar, an arylalkylgroup with 7 to 8 carbon atoms, an arylalkylated N-acylaminoaldoseresidue having an amino group with an acyl group with 2 to 4 carbonatoms and having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylakyl group with7 to 8 carbon atoms, an arylalkylated aldohexuronic acid ester residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylakyl group with 7 to 8 carbon atoms; and Y represents ahalogen atom.

As a result of the above-mentioned reaction between the compounds (II)and (III), the ellipticine derivatives having the following generalformula (Ia) are obtained according to the present invention. ##STR6##wherein R¹, R³, R⁴ and Y.sup.⊖ are the same as defined above and thebond represented by N.sup.⊕ --R⁴ in the general formula (Ia) representsa glycoside bond between a nitrogen atom in the 2-position of theellipticine and a carbon atom in the 1-position of the sugar.

The above-mentioned reaction can be advantageously carried out when thestarting material (III) is readily available, as in the case of chloro-or bromo-sugar. As mentioned above, the ellipticine derivatives (Ia) canbe obtained by heating the reactants (II) and (III) in an organicsolvent such as nitromethane, acetonitrile, propionitrile, benzene,toluene, xylene, dimethylformamide, dimethylsulfoxide, or aniline.Furthermore, this reaction can be effected in the presence of an acidcaptured reagent with or without heating in an organic solvent. Examplesof such acid captured reagents are calcium carbonate, cadmium carbonate,basic zinc carbonate, silver carbonate, and basic copper carbonate. Theuse of these metal compounds allows the reaction yield to be increased.

The resultant ellipticine derivatives (Ia) can be separated andpurified, after the completion of the reaction, by columnchromatography, fractional thin-layer chromatography orrecrystallization. For example, when cadmium carbonate is used as abase, the resultant ellipticine (Ia) can be purified by columnchromatography to such an extent that the content of the cadmium is lessthan 0.1 ppm as determined by atomic absorption spectroscopy.

The above-mentioned ellipticine derivatives (Ia) can be ion-exchangedwith an ion-exchange resin to obtain ellipticine derivatives having thefollowing general formula (Ib): ##STR7## wherein R¹, R³, and R⁴ are thesame as defined above and Z.sup.⊖ is a pharmaceutically acceptableinorganic or organic acid anion.

Examples of the pharmaceutically acceptable inorganic or organic acidanions are those derived from, for example, hydrochloric acid,hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid,phosphoric acid, nitric acid, carbonic acid, acetic acid, propionicacid, oxalic acid, tartaric acid, lactic acid, malic acid, formic acid,fumaric acid, maleic acid, butyric acid, valeric acid, caproic acid,heptanoic acid, capric acid, citric acid, butyric acid, salicylic acid,methane sulfonic acid, succinic acid, aspartic acid, glutamic acid,benzoic acid, and cinnamic acid.

Examples of the ion-exchange resins usable in the above-mentionedion-exchange reaction are commercially available anion exchange resinssuch as Amberlite (available from Organo K.K. Japan), Dowex (availablefrom Dow Chemical Company), and BIO-RAD (available from BIO-RAD ChemicalDivision).

The above-mentioned ellipticine derivatives (Ib) can be furtherhydrolyzed to obtain ellipticine derivatives having the followinggeneral formula (Ic): ##STR8## wherein R³ and Z.sup.⊖ are the same asdefined above, R⁵ represents a hydrogen atom, a hydroxyl group, or analkoxyl group having 1 to 4 carbon atoms, and R⁶ represents an aldoseresidue, a deoxyaldose residue, an N-acylaminoaldose residue having asubstituted acyl group with 2 to 4 carbon atoms bonded to the N atom, analdohexuronic amide residue, an aldohexuronic acid residue, anarylalkylated aldose residue having, substituted for the hydrogen atomof the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms, an arylalkylated deoxyaldose residue having, substitutedfor the hydrogen atom of the hydroxyl group of the sugar, an arylalkylgroup with 7 to 8 carbon atoms, an arylalkylated aldohexuronic amideresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated aldohexuronic acid residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated N-acylaminoaldose residuehaving an amino group substituted with an acyl group with 2 to 4 carbonatoms and having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an arylalkyl group with 7 to 8 carbon atoms.

The above-mentioned hydrolysis can be carried out in the presence of abase, especially a weak base. Examples of such weak bases are ammonia,sodium bicarbonate, potassium bicarbonate, basic sodium phosphate, basicpotassium phosphate, sodium tetraborate (Na₂ B₄ O₇), potassiumtetraborate (K₂ B₄ O₇), lithium carbonate, sodium carbonate, potassiumcarbonate, calcium carbonate, trialkyl amines, calcium hydroxide,aqueous dilute solutions of sodium hydroxide, and potassium hydroxide:Of these bases, the use of ammonia or an aqueous sodium bicarbonatesolution is most preferable under conventional hydrolysis conditionsaccording to sugar chemistry.

On the other hand, the above-mentioned ellipticine derivatives (Ia) canbe hydrolyzed to obtain ellipticine derivatives having the followinggeneral formula (Id): ##STR9## wherein R³, R⁵, R⁶ and Y.sup.⊖ are thesame as defined above.

These ellipticine derivatives (Id) can be ion-exchanged, in the samemanner as mentioned above, to obtain the above-mentioned ellipticinederivatives (Ic). Thus, according to the synthetic methods mentionedabove, the ellipticine derivatives (Ia) to (Id) having sugar, acylatedsugar, or arylalkylated sugar bonded to the nitrogen atom in the2-position of the ellipticine skeleton can be produced.

The above-mentioned ellipticine derivatives (Ib) can be further treatedwith a dealkylating reagent to obtain ellipticine derivatives having thefollowing general formula (Ie): ##STR10## wherein R³ and Z.sup.⊖ are thesame as defined above, R⁷ represents a hydrogen atom, a hydroxyl group,or an acyloxy group having 2 to 7 carbon atoms; and R⁸ represents analdose residue, a deoxyaldose residue, an N-acylaminoaldose residuehaving a substituted acyl group with 2 to 4 carbon atoms bonded to the Natom, an aldohexuronic amide residue, an aldohexuronic acid residue, anacylated aldose residue having, substituted for the hydrogen atom of thehydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbon atomsor an arylacyl group with 7 to 9 carbon atoms, an acylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, an acylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylcyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic acid residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated N-acylaminoaldose residue having an aminogroup substituted with an acyl group with 2 to 4 carbon atoms andhaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms.

Typical examples of the dealkylating agents usable in theabove-mentioned reaction are trialkyl silyl iodide, most preferablytrimethyl silyl iodide. The dealkylating reaction can be carried out inany inert solvent, preferably in a chlorine type or aromatic typehydrocarbon solvent. After the completion of the reaction, the resultantellipticine derivatives (Ie) can be purified by recrystallization,column chromatography, or fractional thin-layer chromatography.Furthermore, the above-mentioned ellipticine derivatives (Ia) can besubjected to dealkylation reaction in the same manner to obtainellipticine derivatives having the following general formula (Ig):##STR11## wherein R³, R⁷, R⁸ and Y.sup.⊖ are the same as defined above.

The resultant ellipticine derivatives (Ig) can be ion-exchanged asmentioned above to obtain the above-mentioned ellipticine derivatives(Ie).

The above-mentioned ellipticine derivatives (Ie) can be furtherhydrolyzed to obtain ellipticine derivatives having the general formula(If): ##STR12## wherein R³ and Z.sup.⊖ are the same as defined above, R⁹represents a hydrogen atom or a hydroxyl group, and R¹⁰ represents analdose residue, a deoxyaldose residue, an N-acylaminoaldose residuehaving a substituted acyl group with 2 to 4 carbon atoms bonded to the Natom, an aldohexuronic amide residue, or an aldohexuronic acid residue.The bases usable in the hydrolysis are the same as mentioned above. Theabove-mentioned ellipticine derivatives (Ig) can be hydrolyzed in thesame manner as mentioned above to obtain ellipticine derivatives havingthe general formula (Ih): ##STR13## wherein R³, R⁹, R¹⁰, and Y.sup.⊖ arethe same as defined above.

The ellipticine derivatives (Ih) can be ion-exchanged as mentionedabove, to form the above-mentioned ellipticine derivatives (If).

Furthermore, the above-mentioned ellipticine derivatives (Ic) can befurther dealkylated as mentioned above to obtain ellipticine derivativeshaving the general formula (If).

The ellipticine derivatives (Id) can be further dealkylated to form theellipticine derivative having the above-mentioned general formula (Ih).

As mentioned above, the above-mentioned various derivatives (Ib) to (Ih)can be obtained by the hydrolysis, dealkylation, and/or ion-exchangingfrom the ellipticine derivatives (Ia) obtained from the reactions of theellipticine derivatives (II) with the aldose derivatives (III).

The glycoside bond between the nitrogen atom in the 2-position of theellipticine derivatives and the carbon atom in the 1-position of thesugar can be confirmed by nuclear magnetic resonance (NMR) spectrum,mass spectrum, and elementary analysis. Thus, when the signal of thehydrogen atom in the 1-position of the sugar (i.e., anomeric hydrogen)is irradiated, the signal intensity of the hydrogen atom in the 1- and3-position of the ellipticine derivative is increased (NOE). Therefore,the bonding of the carbon atom in the 1-position of the sugar to thenitrogen atom in the 2-position of the ellipticine derivatives can beconfirmed.

Examples of the substituent R² in the abovementioned general formula (I)are the residues of aldotetroses such as D-erythrose, D-threose,L-erythrose, L-threose, di-O-acetyl-D-erythrose, di-O-acetyl-D-threose,di-O-acetyl-L-erythrose, di-O-acetyl-L-threose,di-O-benzoyl-D-erythrose, di-O-benzoyl-D-threose,di-O-benzoyl-L-erythrose, di-O-benzoyl-L-threose,di-O-benzyl-D-erythrose, di-O-benzyl-D-threose, di-O-benzyl-L-erythrose,and di-O-benzyl-L-threose; the residues of aldopentoses such asD-ribose, D-xylose, L-ribose, L-xylose, D-arabinose, D-lyxose,L-arabinose, L-lyxose, tri-O-acetyl-D-ribose, tri-O-acetyl-D-xylose,tri-O-acetyl-L-ribose, tri-O-acetyl-L-xylose, tri-O-acetyl-D-arabinose,tri-O-acetyl-D-lyxose, tri-O-acetyl-L-arabinose, tri-O-acetyl-L-lyxose,tri-O-benzoyl-D-ribose, tri-O-benzoyl-D-xylose, tri-O-benzoyl-L-ribose,tri-O-benzoyl-L-xylose, tri-O-benzoyl-D-arabinose,tri-O-benzoyl-D-lyxose, tri-O-benzoyl-L-arabinose,tri-O-benzoyl-L-lyxose, tri-O-benzyl-D-ribose, tri-O-benzyl-D-xylose,tri-O-benzyl-L-ribose, tri-O-benzyl-L-xylose, tri-O-benzyl-D-arabinose,tri-O-benzyl-D-lyxose, tri-O-benzyl-L-arabinose, andtri-O-benzyl-L-lyxose; the residues of aldohexoses such as D-glucose,D-mannose, L-glucose, L-mannose, D-allose, D-altrose, L-allose,L-altrose, D-gulose, D-idose, L-gulose, L-idose, D-galactose, D-talose,L-galactose, L-talose, tetra-O-acetyl-D-glucose,tetra-O-acetyl-D-mannose, tetra-O-acetyl-L-glucose,tetra-O-acetyl-L-mannose, tetra-O-acetyl-D-allose,tetra-O-acetyl-D-altrose, tetra-O-acetyl-L-allose,tetra-O-acetyl-L-altrose, tetra-O-acetyl-D-gulose,tetra-O-acetyl-D-idose, tetra-O-acetyl-L-gulose, tetra-O-acetyl-L-idose,tetra-O-acetyl-D-galactose, tetra-O-acetyl-D-talose,tetra-O-acetyl-L-galactose, tetra-O-acetyl-L-talose,tetra-O-benzoyl-D-glucose, tetra-O-benzoyl-D-mannose,tetra-O-benzoyl-L-glucose, tetra-O-benzoyl-L-mannose,tetra-O-benzoyl-D-allose, tetra-O-benzoyl-D-altrose,tetra-O-benzoyl-L-allose, tetra-O-benzoyl-L-altrose,tetra-O-benzoyl-D-gulose, tetra-O-benzoyl-D-idose,tetra-O-benzoyl-L-gulose, tetra-O-benzoyl-L-idose,tetra-O-benzoyl-D-galactose, tetra-O-benzoyl-D-talose,tetra-O-benzoyl-L-galactose, tetra-O-benzoyl-L-talose,tetra-O-benzyl-D-glucose, tetra-O-benzyl-D-mannose,tetra-O-benzyl-L-glucose, tetra-O-benzyl-L-mannose,tetra-O-benzyl-D-allose, tetra-O-benzyl-D-altrose,tetra-O-benzyl-L-allose, tetra-O-benzyl-L-altrose,tetra-O-benzyl-D-gulose, tetra-O-benzyl-D-idose,tetra-O-benzyl-L-gulose, tetra-O-benzyl-L-idose,tetra-O-benzyl-D-galactose, tetra-O-benzyl-D-talose,tetra-O-benzyl-L-galactose, and tetra-O-benzyl-L-talose, the residues of2- or 6-deoxyaldohexoses such as D-quinovose (i.e., 6-deoxy-D-glucose)L-rhamnose (i.e., 6-deoxy-L-mannose), L-fucose (i.e.,6-deoxy-L-galactose), D-fucose (i.e., 6-deoxy-D-galactose),6-deoxy-D-allose, 6-deoxy-D-altrose, 6-deoxy-D-gulose, 6-deoxy-L-talose,tri-O-acetyl-D-quinovose, tri-O-acetyl-L-rhamnose,tri-O-acetyl-L-fucose, tri-O-acetyl-D-fucose,6-deoxy-tri-O-acetyl-D-allose, 6-deoxy-tri-O-acetyl-L-altrose,6-deoxy-tri-O-acetyl-D-gulose, 6-deoxy-tri-O-acetyl-L-talose,tri-O-benzoyl-D-quinovose, tri-O-benzoyl-L-rhamnose,tri-O-benzoyl-L-fucose, trio-O-benzoyl-D-fucose,6-deoxy-tri-O-benzoyl-D-allose, 6-deoxy-tri-O-benzoyl-D-altrose,6-deoxy-tri-O-benzoyl-D-gulose, 6-deoxy-tri-O-benzoyl-L-talose,tri-O-benzyl-D-quinavose, tri-O-benzyl-L-rhamnose,tri-O-benzyl-L-fucose, tri-O-benzyl-D-fucose,6-deoxy-tri-O-benzyl-D-allose, 6-deoxy-tri-O-benzyl-D-altrose,6-deoxy-tri-O-benzyl-D-gulose, 6-deoxy-tri-O-benzyl-L-talose,2-deoxy-D-glucose, 2-deoxy-D-gulose, 2-deoxy-D-galactose,2-deoxy-tri-O-acetyl-D-glucose, 2-deoxy-tri-O-acetyl-D-gulose,2-deoxy-tri-O-acetyl-D-galactose, 2-deoxy-tri-O-benzoyl-D-glucose,2-deoxy-tri-O-benzoyl-D-gulose, 2-deoxy-tri-O-benzoyl-D-galactose,2-deoxy-tri-O-benzyl-D-glucose, 2-deoxy-tri-O-benzyl-D-gulose, and2-deoxy-tri-O-benzyl-D-galactose; the residues of 2- or5-deoxyaldopentoses such as 2-deoxy-D-ribose, 5-deoxy-L-arabinose,5-deoxy-D-xylose, 5-deoxy-D-lyxose, 5-deoxy-D-ribose,2-deoxy-di-O-acetyl-D-ribose, 5-deoxy-di-O-acetyl-L-arabinose,5-deoxy-di-O-acetyl-D-xylose, 5-deoxy-di-O-acetyl-D-lyxose,5-deoxy-di-O-acetyl-D-ribose, 2-deoxy-di-O-benzoyl-D-ribose,2-deoxy-di-O-benzoyl-D-arabinose, 5-deoxy-di-O-benzoyl-D-xylose,5-deoxy-di-O-benzoyl-D-lyxose, 5-deoxy-di-O-benzoyl-D-ribose,2-deoxy-di-O-benzyl-D-ribose, 5-deoxy-di-O-benzyl-L-arabinose,5-deoxy-di-O-benzyl-D-xylose, 5-deoxy-di-O-benzyl-D-lyxose,5-deoxy-di-O-benzyl-D-ribose; the residues of N-acylaminoaldoses such asN-acetyl-D-galactosamine (2-acetamido-2-deoxy-D-galactose),N-acetyl-D-glucosamine(2-acetamido-2-deoxy-D-glucose),N-acetyl-D-gulosamine(2-acetamido-2-deoxy-D-gulose),N-acetyl-D-talosamine(2-acetamido-2-deoxy-D-talose),N-acetyl-D-mannosamine(2-acetamido-2-deoxy-D-mannose),N-acetyl-D-kanosamine(6-acetamido-6-deoxy-D-glucose),N-acetyl-D-fucosamine(2-acetamido-2,6-dideoxy-L-galactose),N-acetyl-L-fucosamine,N-acetyl-mycosamine(3-acetamido-3,6-dideoxy-D-mannose),N-acetyl-pneumosamine(2-acetamido-2,6-dideoxy-L-talose),N-acetyl-tri-O-acetyl-D-galactosamine,N-acetyl-tri-O-acetyl-D-glucosamine, N-acetyl-tri-O-acetyl-D-gulosamine,N-acetyl-tri-O-acetyl-D-talosamine, N-acetyl-tri-O-acetyl-D-mannosamine,N-acetyl-tri-O-acetyl-kanosamine, N-acetyl-di-O-acetyl-D-fucosamine,N-acetyl-di-O-acetyl-L-fucosamine, N-acetyl-di-O-acetyl-mycosamine,N-acetyl-di-O-acetyl-pneumosamine,N-acetyl-tri-O-benzoyl-D-galactosamine,N-acetyl-tri-O-benzoyl-D-glucosamine,N-acetyl-tri-O-benzoyl-D-gulosamine,N-acetyl-tri-O-benzoyl-D-talosamine,N-acetyl-tri-O-benzoyl-D-mannosamine, N-acetyl-tri-O-benzoyl-kanosamine,N-acetyl-di-O-benzoyl-D-fucosamine, N-acetyl-di-O-benzoyl-L-fucosamine,N-acetyl-di-O-benzoyl-mycosamine, N-acetyl-di-O-benzoyl-pneumosamine,N-acetyl-tri-O-benzyl-D-galactosamine,N-acetyl-tri-O-benzyl-D-glucosamine, N-acetyl-tri-O-benzyl-D-gulosamine,N-acetyl-tri-O-benzyl-D-talosamine, N-acetyl-tri-O-benzyl-D-mannosamine,N-acetyl-tri-O-benzyl-kanosamine, N-acetyl-di-O-benzyl-D-fucosamine,N-acetyl-di-O-benzyl-L-fucosamine, N-acetyl-di-O-benzyl-mycosamine,N-acetyl-di-O-benzyl-pneumosamine; the residues of aldohexuronic acidderivatives such as L-iduronic acid, D-galacturonic acid, D-glucuronicacid, L-glucuronic acid, D-mannuronic acid, methyltri-O-acetyl-L-iduronate, methyl tri-O-acetyl-D-galacturonate, methyltri-O-D-glucuronate, methyl tri-O-acetyl-L-glucuronate, methyltri-O-acetyl-D-mannuronate, methyl tri-O-benzoyl-L-iduronate, methyltri-O-benzoyl-D-galacturonate, methyl tri-O-benzoyl-D-glucuronate,methyl tri-O-benzoyl-L-glucuronate, methyl tri-O-benzyl-L-iduronate,methyl tri-O-benzyl-D-galacturonate, methyl tri-O-benzyl-D-glucuronate,and methyl tri-O-benzyl-L-glucuronate; and the residues of aldohexuronicamides such as L-iduronic amide, D-galacturonic amide, D-glucuronicamide, L-glucuronic amide, D-mannuronic amide, tri-O-acetyl-L-iduronicamide, tri-O-acetyl-D-galacturonic amide, tri-O-acetyl-D-glucuronicamide, tri-O-acetyl-L-glucuronic amide tri-O-acetyl-D-mannuronic amide,tri-O-benzoyl-L-iduronic amide, tri-O-benzoyl-D-galacturonic amide,tri-O-benzoyl-D-glucuronic amide, tri-O-benzoyl-L-glucuronic amide,tri-O-benzoyl-D-mannuronic amide, tri-O-benzyl-L-iduronic amide,tri-O-benzyl-D-galacturonic amide, tri-O-benzyl-D-glucuronic amide,tri-O-benzyl-L-glucuronic amide, and tri-O-benzyl-D-mannuronic amide.

The ellipticine derivatives according to the present invention aregenerally disclosed and decomposed within a wide temperature rangeduring the measurement of melting points and, therefore, do not exhibitclear melting points.

The ellipticine derivatives having the general formula (I) (and thegeneral formulae (Ia) to (Ih), according to the present invention haveremarkable antineoplastic or antitumor effects against mouse lymphoidleukemia L 1210 as shown in the Examples hereinbelow. It is consideredthat the present ellipticine derivatives are effective antineoplastic orantitumor agents in view of the fact that the antineoplastic orantitumor activity of the present ellipticine derivatives is superior tothat of Celiptium used as a control, which is clinically administered topatients with mammary cancer.

When the present ellipticine derivatives are used as an antineoplasticor antitumor agent, they can be used in any form, for example, in theform of injection such as endovenous, intramuscular, or hypodermicinjection, in the form of oral administration drugs such as tablets,granulars, powder, or troches, or in the form of endermic drugs such asvaginal or rectal suppository, or ointments.

In the practice of the formulation, any conventional andpharmaceutically acceptable ingredients including diluents, carriers,excipients, binders, and vehicles can be used. Pharmaceuticallyacceptable vehicles such as atoxic liquid oil can be used as asuspending agent.

REMARKS

The compound Nos. 1 to 14 in Table 1 have the following general formula:##STR14##

The compound Nos. 15 to 28 in Table 1 have the following generalformula: ##STR15##

The compound Nos. 29 to 52 in Table 1 have the following generalformula: ##STR16##

The compound Nos. 53 to 112 in Table 1 have the following generalformula: ##STR17##

The compound Nos. 113 to 172 in Table 2 have the following generalformula:

EXAMPLES

The present invention now will be further illustrated by, but is by nomeans limited to, the following examples.

In the examples, the following abbreviations and commercial products areused.

Ac: Acetyl group

Bz: Benzoyl group

Bn: Benzyl group

BIO-RAD Ag1-X8: Ion exchange resin available from BIO-RAD ChemicalDivision

Sephadex LH20: Gel infiltration resin available from Pharmacia FineChemicals A.G.

Kieselgel 60: Silicagel available from Merck & Co., Inc.

Furthermore, the analytical data in the Examples were obtained asfollows:

UV absorption spectrum: Shimadzu UV-250 or Beckman DU-8Spectrophotometer

IR absorption spectrum: Hitachi 260-10 or Nicolet 5DX(FT-IR)

Specific rotatory power [α]_(D) : Perkin-Elmer 241 Polarimeter or JASCODIP-181 Digital Polarimeter

Proton NMR: Nicolet NT-360, Nicolet NT-300, or Nippon Denshi GX-270

Mass spectrum: SIMS method (partial chemical ionization (C.I.) method)

In Examples 96, 97, 109, 110, and 111, molecular ellipticity in waterwas used instead of [α]_(D).

[α]_(D) was measured by the following conditions:

    ______________________________________                                        Example 1 to 12    at 29° C.                                           Examples 13, 14    at 25° C.                                           Examples 15 to 28  at 31° C.                                           Examples 29 to 52  at 26° C. in methanol                               Example 53         at 29° C.                                           Example 54         at 26° C.                                           Examples 55 to 61  at 29° C.                                           Examples 62 to 95                                                                                in 1% CF.sub.3 COOH--H.sub.2 O at 25° C.            Examples 98 to 106                                                            ______________________________________                                    

another condition was shown in Tables 1 and 2. In Tables 1 and 2, thefollowing abbreviations are used.

MeOH: methanol

EtOH: ethanol

DMSO: dimethylsulfoxide.

EXAMPLE 1 Preparation of2-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)ellipticinium bromide##STR19##

A 300 mg amount of ellipticine, 860 mg of2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide, and 1.190 g ofcadmium carbonate were suspended in 37 ml of nitromethane and thesolution was heated under reflux for 20 minutes. After cooling theinsoluble matter was filtered and washed with a small amount ofnitromethane. The nitromethane layer was concentrated in vacuo to obtain1.4 g of the crystalline residue.

The residue obtained above was subjected to silicagel columnchromatography using, as an elute solvent, a mixture of chloroform andmethanol (95:5). Thus, 810 mg of the crystalline compound was obtained.This compound contained a small amount of impurities and, therefore, thecompound was purified by column chromatography (Sephadex LH20, solvent:methanol). As a result, 567 mg of the desired compound was obtained.

The analytical data of the resultant compound are shown in Table 1.

EXAMPLE 2 Preparation of 2-β-D-galactopyranosylellipticinium bromide##STR20##

A 250 mg amount of the ellipticine derivative obtained in Example 1 wasdissolved in 50 ml of methanol saturated with gaseous ammonia and wasallowed to stand overnight in a refrigerator. The insoluble matter wasfiltered and then, the resultant solution was concentrated to obtain 105mg of the desired compound.

The results are shown in Table 1.

EXAMPLE 3 to 5

The following ellipticine derivatives were prepared in the same manneras in Examples 1 and 2.

Example 3: 2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)ellipticiniumbromide.

Example 4: 2-β-D-ribofuranosylellipticinium bromide.

Example 5: 2-(b 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)ellipticiniumbromide.

The results are shown in Table 1.

EXAMPLE 6

Preparation of 2-β-D-glucopyranosylellipticinium acetate ##STR21##

A 98 mg amount of the ellipticinium derivative obtained in Example 5 wasdissolved in a dimethylformamide-water solvent and was then passedthrough an ion exchange resin column (BIO-RAD, AG1-X8, acetate type).The column was eluted with water. Thus, 111 mg of2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)ellipticinium acetate wasobtained. To the resultant compound, 15 ml of methanol saturated withgaseous ammonia was added and the mixture was allowed to stand at atemperature of 0° C. to 5° C. for 15 hours. After concentrating, a smallamount of methanol was added to the concentrated mixture and, then,ethyl acetate was added to precipitate 52 mg of the desired compound inthe form of powder.

EXAMPLES 7 TO 12

The following ellipticine derivatives were prepared in the same manneras in Examples 1 and 2.

Example 7: 2-(2,3,4-tri-O-acetyl-β-D-fucopyranosyl)ellipticiniumbromide.

Example 8: 2-β-D-fucopyranosylellipticinium bromide.

Example 9: 2-(2,3,4-tri-O-acetyl-β-L-fucopyranosyl)ellipticiniumbromide.

Example 10: 2-β-L-fucopyranosylellipticinium bromide.

Example 11: 2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)ellipticiniumbromide.

Example 12: 2-α-L-rhamnopyranosylellipticinium bromide.

The results are shown in Table 1.

EXAMPLE 13 Preparation of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)ellipticinium chloride##STR22##

A 70 mg amount of ellipticine, 70 mg of cadmium carbonate, and 230 mg of2,3,5-tri-O-benzoyl-α-D-xylofuranosyl chloride were suspended in 7 ml ofnitromethane and the suspension was heated under reflux for 10 minutes.The insoluble matter was filtered and the resultant solution wasconcentrated. The residue thus obtained was subjected to silicagelcolumn chromatography (Kieselgel 60, 50 ml) and the column was eluted bya solvent mixture of methylene chloride and methanol (90:10). Theresultant product was then purified by gel filtration chromatography(Sephadex LH-20, 2.0 cmφ×18 cm). Thus, 70.2 mg of the desired productwas eluted with methanol.

The results are shown in Table 1.

When 2,3,5-tri-O-benzoyl-α-L-xylofuranosyl chloride was used,2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)ellipticinium chloride wasobtained.

EXAMPLE 14 Preparation of 2-β-D-xylofuranosylellipticinium chloride##STR23##

A 55 mg amount of 2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)ellipticiniumchloride was dissolved in 9 ml of methanol saturated with gaseousammonia. The solution was allowed to stand for 15 hours at roomtemperature. After concentrating, the product was precipitated from amixture of methanol and ethyl acetate and separated. Thus, 20.2 mg ofthe desired compound was obtained.

The results are shown in Table 1.

Similarly, when 2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)ellipticiniumchloride was used, 2-β-L-xylofuranosylellipticinium chloride wasobtained.

EXAMPLE 15 Preparation of2-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-9-methoxyellipticiniumbromide ##STR24##

A 100 mg amount of 9-methoxyellipticine, 377 mg (3 equivalent) ofα-bromoaceto-D-galactose, and 130 mg of cadmium carbonate were suspendedin 15 ml of nitromethane and the mixture was heated under reflux for 15minutes.

The insoluble matter was filtered and the resultant solution wasconcentrated to obtain the crystalline residue. The residue wasdissolved in methanol and then, was purified with Sephadex LH-20 column(diameter: 4.6 cm, height: 30 cm, methanol as an eluent). Thus, 219 mgof the desired compound was obtained.

The results are shown in Table 1.

EXAMPLE 16 Preparation of 2-β-D-galactopyranosyl-9-methoxyellipticiniumbromide ##STR25##

A 19 ml amount of methanol saturated with gaseous ammonia was added to187 mg of the ellipticinium tetraacetate derivative obtained in Example15 and the mixture was allowed to stand at a temperature of 0° C. for 15hours. The insoluble matter was filtered and the resultant solution wasconcentrated to obtain the crystalline residue. The residue thusobtained was recrystallized from a mixture of methanol and ethylacetate. Thus, 30 mg of the desired compound in the form of yellowcrystal was obtained.

The results are shown in Table 1.

EXAMPLES 17 to 26

The following ellipticine derivatives were prepared in the same manneras in Examples 15 and 16.

Example 17:2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-9-methoxyellipticiniumbromide.

Example 18: 2-β-D-ribofuranosyl-9-methoxyellipticinium bromide.

Example 19:2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-9-methoxyellipticiniumbromide.

Example 20: 2-β-D-glucopyranosyl-9-methoxyellipticinium bromide.

Example 21:2-(2,3,4-tri-O-acetyl-β-D-fucopyranosyl)-9-methoxyellipticinium bromide.

Example 22: 2-β-D-fucopyranosyl-9-methoxyellipticinium bromide.

Example 23:2-(2,3,4-tri-O-acetyl-β-L-fucopyranosyl)-9-methoxyellipticinium bromide.

Example 24: 2-β-L-fucopyranosyl-9-methoxyellipticinium bromide.

Example 25:2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-methoxyellipticiniumbromide.

EXample 26: 2-α-L-rhamnopyranosyl-9-methoxyellipticinium bromide.

The results are shown in Table 1.

EXAMPLE 27 Preparation of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)-9-methoxyellipticiniumchloride ##STR26##

A 70 mg amount of 9-methoxyellipticine, 70 mg of cadmium carbonate, and230 mg of 2,3,5-tri-O-benzoyl-α-D-xylofuranosyl chloride were suspendedin 7 ml of nitromethane and the suspension was heated under reflux for10 minutes. The insoluble matter was filtered and the resultant solutionwas concentrated. The residue thus obtained was subjected to silicagelcolumn chromatography (Kieselgel 60, 50 ml) and the column was eluted bya solvent mixture of methylene chloride and methanol (90:10). Theresultant product was then purified by gel filtration chromatography(Sephadex LH-20, 2.0 cmφ×20 cm, methanol). Thus, 65 mg of the desiredproduct was obtained.

The results are shown in Table 1.

When 2,3,5-tri-O-benzoyl-α-L-xylofuranosyl chloride was used,2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)-9-methoxyellipticiniumchloride was obtained.

EXAMPLE 28 Preparation of 2-β-D-xylofuranosyl-9-methoxyellipticiniumchloride ##STR27##

A 51 mg amount of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)-9-methoxyellipticiniumchloride was dissolved in 8 ml of methanol saturated with gaseousammonia. The solution was allowed to stand for 15 hours at roomtemperature. After concentrating, the residue was dissolved in methanoland the product was precipitated from methanol solution with ethylacetate. Thus, 24 mg of the desired compound was obtained.

The results are shown in Table 1.

Similarly, when2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)-9-methoxyellipticiniumchloride was used, 2-β-L-xylofuranosyl-9-methoxyellipticinium chloridewas obtained.

EXAMPLE 29 Preparation of9-acetoxy-2-(2,3-di-O-benzoyl-β-D-erythrofuranosyl)ellipticiniumchloride ##STR28##

A 172 mg amount of 9-acetoxyellipticine, 170 mg of cadmium carbonate,and 309 mg of 2,3-di-O-benzoyl-D-erythrofuranosyl chloride were added to17 ml of nitromethane methane and the mixture was heated under refluxfor 10 minutes. The insoluble matter was filtered and washed withnitromethane. The nitromethane solution was concentrated to obtain theoily residue.

The oily residue obtained above was subjected to column chromatographyusing 200 ml of silicagel (Kieselgel 60) and was eluted with a mixtureof chloroform and methanol (91:9-87:13) to obtain the yellowish browncompound. The yellowish brown compound was dissolved in 30 ml ofmethanol. The resultant solution was subjected to column chromatographyusing Sephadex LH-20 (42 cm×2.5 cmφ) and was eluted with methanol.

The resultant yellowish brown layer was concentrated to obtain 128 mg(35% yield) of the desired compound. The results are shown in Table 1.

When 2,3-di-O-benzoyl-L-erythrofuranosyl chloride was used instead of2,3-di-O-benzoyl-D-erythrofuranosyl chloride,9-acetoxy-2-(2,3-di-O-benzoyl-β-L-erythrofuranosyl)ellipticiniumchloride was obtained.

EXAMPLE 30 Preparation of9-acetoxy-2-(2,3-di-O-benzoyl-5-deoxy-β-D-ribofuranosyl)ellipticiniumchloride ##STR29##

A 300 mg amount of 9-acetoxyellipticine, 708 mg of2,3-di-O-benzoyl-5-deoxy-D-ribofuranosyl chloride, and 339 mg of cadmiumcarbonate were suspended in 30 ml of nitromethane and the mixture washeated under reflux for 15 minutes. The insoluble matter was separatedby filtration and the solvent was distilled off in vacuo. Thus, 820 mgof the residue was obtained. The residue was dissolved in a 3%methanol-chloroform solvent. The solution was subjected to columnchromatography using 600 ml of silicagel and was eluted with a solventmixture of methanol and chloroform (8:92). Thus, 289 mg of the productwas obtained.

A 192 mg amount of the product was then purified by dissolving theproduct in methanol, followed by subjected to column chromatographyusing Sephadex LH-20 (5 cmφ×28 cm). 151 mg of the desired compound inthe form of yellowish brown powder was obtained by elution withmethanol.

The results are shown in Table 1.

EXAMPLES 31 AND 32

The following ellipticine derivatives were prepared in the same manneras in Example 30.

Example 31:9-Acetoxy-2-(2,3-di-O-benzoyl-5-deoxy-α-L-arabinofuranosyl)ellipticiniumchloride

Example 32:9-Acetoxy-2-(3,5-di-O-p-toluoyl-2-deoxy-β-D-ribofuranosyl)ellipticiniumchloride

The results are shown in Table 1.

EXAMPLE 33 Preparation of9-acetoxy-2-(2,3-di-O-benzyl-5-deoxy-β-L-arabinofuranosyl)ellipticiniumchloride ##STR30##

A 242 mg amount of 9-acetoxyellipticine, 394 mg of2,3-di-O-benzyl-5-deoxy-α-L-arabinofuranosyl chloride, and 242 mg ofcadmium carbonate were suspended in 25 ml of nitromethane and themixture was heated under reflux for 10 minutes. After removing theprecipitate, the resultant solution was concentrated. The residue thusobtained was subjected to column chromatography using silicagel(Kieselgel 60, 300 ml) and was eluted with a solvent mixture ofmethylene chloride and methanol (93:7-91:9). The eluted fraction wasthen subjected to gel filtration column chromatography using SephadexLH-20 (4.5 cmφ×22 cm) and was eluted with methanol.

As a result, 310 mg (61% yield) of the desired compound was obtained inthe form of orange powder.

The results are shown in Table 1.

EXAMPLE 34 Preparation of9-acetoxy-2-(2,3,5-tri-O-benzoyl-D-lyxofuranosyl)ellipticinium chloride##STR31##

A 324 mg amount of 9-acetoxyellipticine, 320 mg of cadmium carbonate and870 mg of 2,3,5-tri-O-benzoyl-D-lyxofuranosyl chloride were suspended in32 ml of nitromethane and the mixture was heated under reflux for 7minutes. After the precipitate was removed by filtration, the resultantresidue was subjected to column chromatography using silicagel(Kieselgel 60, 400 ml) and was eluted with 3.5 liters of a solventmixture of methylene chloride and methanol (94:6-90:10). The elutedfraction was concentrated and the resultant concentrate was thensubjected to gel filtration column chromatography using Sephadex LH 20(4.5 cmφ×44 cm) and was eluted with methanol.

As a result, 677 mg of the desired compound was obtained.

The product thus obtained had two stereoisomers (i.e.,1',2'-trans-isomer and 1',2'-cis-isomer) to the 1-position of the sugar.The ratio of 1',2'-trans/1', 2'-cis was 6/1 when determined by NMRspectrum of the hydrogen atom in the 1-position of the sugar.

When 2,3,5-tri-O-benzoyl-L-lyxofuranosyl chloride was used instead ofthe D-lyxofuranosyl chloride,9-acetoxy-2-(2,3,5-tri-O-benzoyl-L-lyxofuranosyl)ellipticinium chloridewas obtained.

EXAMPLE 35 Preparation of9-acetoxy-2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)ellipticiniumchloride ##STR32##

A 215 mg amount of 9-acetoxyellipticine, 713 mg of2,3,5-tri-O-benzoyl-α-D-xylofuranosyl chloride, and 243 mg of cadmiumcarbonate were suspended in 22 ml of nitromethane. The suspension wastreated in the same manner as in Example 34 by using silicagel columnchromatography (600 ml, 3% methanol-chloroform) and gel filtrationcolumn chromatography (Sephadex LH-20, 4.2 cmφ×37 cm, methanol).

As a result, 304 mg of the desired compound was obtained. The resultsare shown in Table 1.

When 2,3,5-tri-O-benzoyl-α-L-xylofuranosyl chloride was used instead ofthe D-xylofuranosyl chloride,9-acetoxy-2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)ellipticiniumchloride was obtained.

EXAMPLE 36 TO 39

The following ellipticine derivatives were prepared in the same manneras in Example 35.

Example 36:

9-Acetoxy-2-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)ellipticiniumbromide.

9-Acetoxy-2-(2,3,5-tri-O-benzoyl-α-L-arabinofuranosyl)ellipticiniumbromide.

Example 37:9-Acetoxy-2-(2,3,5-tri-O-benzoyl-β-L-ribofuranosyl)ellipticiniumbromide.

Example 38:9-Acetoxy-2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)ellipticiniumbromide.

Example 39*:

9-Acetoxy-2-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)ellipticiniumbromide.

9-Acetoxy-2-(2,3,5-tri-O-benzyl-β-L-arabinofuranosyl)ellipticiniumbromide.

The results are shown in Table 1.

EXAMPLE 40 Preparation of9-acetoxy-2-(2,3,4-tri-O-acetyl-D-xylopyranosyl)ellipticinium bromide##STR33##

A 150 mg amount of 9-acetoxyellipticine, 335 mg of2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide, and 169 mg of cadmiumcarbonate were suspended in 15 ml of nitromethane and the mixture washeated under reflux for 15 minutes. The mixture was then treated withsilicagel column chromatography 180 g, elution solvent: 4-8%methanol-chloroform) and gel filtration column chromatography (SephadexLH-20, 150 g, methanol) in the same manner as mentioned above. Thus, 188mg of the desired compound was obtained.

The resultant compound had two types of stereoisomers against the1-position of the sugar in the ratio of 1',2'-trans(β-form)/1',2'-cis(α-form) of 2.5/1.0. In Table 1, NMR data of the mainproduct (i.e, β-form) are shown and the other data represent those ofthe mixture of the α- and β-form. The NMR spectra of the α-form are asfollows:

1.97, 2.19, 2.27 (each 3H,s), 3.87 (2H,m) 4.84 (1H,m), 5.21 (1H,m), 5.39(1H,brs) 6.60 (1H,brs), 8.27 (1H,d,J=2 Hz), 10.12(1H,s).

EXAMPLE 41 Preparation of9acetoxy-2-(2,3,4-tri-O-acetyl-L-xylopyranosyl)ellipticinium bromide##STR34##

The desired compound was prepared by using2,3,4-tri-O-acetyl-α-L-xylopyranosyl bromide in the same manner as inExample 40. This compound also had two types of stereoisomers on the1-position of the sugar at a ratio of 1',2'-trans (β-form)/1',2'-cis(α-form)=6.8/1.

EXAMPLE 42 Preparation of9-acetoxy-2-(2,3,4-tri-O-acetyl-α-D-arabinopyranosyl)ellipticiniumbromide ##STR35##

A 200 mg amount of 9-acetoxyellipticine, 446 mg of2,3,4-tri-O-acetyl-β-D-arabinopyranosyl bromide, and 226 mg of cadmiumcarbonate were suspended in 20 ml of nitromethane and the mixture washeated under reflux for 15 minutes. After removing the insoluble matter,the reaction mixture was concentrated. A small amount of methanol wasadded to the residue obtained above to crystallize the product. Thecrystal was filtered and, after washing with chloroform, was dissolvedin methanol. The methanol solution thus obtained was subjected to gelfiltration column chromatography (Sephadex LH-20, 3.5 cmφ×40 cm) and waseluted with methanol. Thus, 254 mg of the desired compound was obtainedin the form of red powder.

The results are shown in Table 1.

Similarly, when 2,3,4-tri-O-acetyl-β-L-arabinopyranosyl bromide wasused, 9-acetoxy-2-(2,3,4-tri-O-acetyl-α-L-arabinopyranosyl)ellipticiniumbromide was obtained.

EXAMPLES 43 AND 44

The following ellipticine derivatives were prepared in the same manneras in Example 42.

Example 43:

9-Acetoxy-2-(2,3,4-tri-O-acetyl-β-D-ribopyranosyl)ellipticinium bromide.

9-Acetoxy-2-(2,3,4-tri-O-acetyl-β-L-ribopyranosyl)ellipticinium bromide.

Example 44:

9-Acetoxy-2-(2,3,4-tri-O-acetyl-α-D-lyxopyranosyl)ellipticiniumchloride.

9-Acetoxy-2-(2,3,4-tri-O-acetyl-α-L-lyxopyranosyl)ellipticiniumchloride.

The results are shown in Table 1.

EXAMPLE 45 Preparation of9-acetoxy-2-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)ellipticiniumbromide ##STR36##

The desired compound 197 mg was prepared from 150 mg of9-acetoxyellipticine, 600 mg of 2,3,4,6-tetra-O-acetyl-D-mannopyranosylbromide, and 165 mg of cadmium carbonate in the same manner as mentionedabove.

The results are shown in Table 1.

Similarly,9-acetoxy-2-(2,3,4,6-tetra-O-acetyl-α-L-mannopyranosyl)ellipticiniumbromide was obtained from 2,3,4,6-tetra-O-acetyl-L-mannopyranosylbromide.

EXAMPLE 46 TO 49

The following ellipticine derivatives were prepared in the same manneras in Example 45. The results are shown in Table 1.

Example 46:

9-Acetoxy-2-(2,3,4,6-tetra-O-acetyl-β-D-allopyranosyl)ellipticiniumbromide.

9-Acetoxy-2-(2,3,4,6-tetra-O-acetyl-β-L-talopyranosyl)ellipticiniumbromide.

Example 47:

9-Acetoxy-2-(2,3,4,6-tetra-O-acetyl-α-D-talopyranosyl)ellipticiniumbromide.

9-Acetoxy-2-(2,3,4,6-tetra-O-acetyl-α-L-talopyranosyl)ellipticiniumbromide.

Example 48:9-Acetoxy-2-(2,3,4,6-tetra-O-acetyl-β-L-galactopyranosyl)ellipticiniumbromide.

Example 49:9-Acetoxy-2-(2,3,4,6-tetra-O-acetyl-β-L-glucopyranosyl)ellipticiniumbromide.

EXAMPLE 50 Preparation of9-acetoxy-2-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)ellipticiniumchloride ##STR37##

A 300 mg amount of 9-acetoxyellipticine, 300 mg of cadmium carbonate,and 917 mg of 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosylchloride were suspended in 30 ml of nitromethane and the mixture washeated under reflux for 10 minutes. After removing the precipitate byfiltration, the resultant residue was dissolved in methanol. Themethanol solution was subjected to gel filtration column chromatography(Sephadex LH-20, 4,0 cmφ×35 cm), and was eluted with methanol. Thus, 219mg (33% yield) of the desired compound was obtained.

The results are shown in Table 1.

EXAMPLE 51 Preparation of9-acetoxy-2-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-galactopyranosyl)ellipticiniumbromide

The desired compound was prepared in the same manner as in Example 50.

EXAMPLE 52 Preparation of 9-acetoxy-2-(methyl2,3,4-tri-O-acetyl-β-D-glucuronopyranosyl)ellipticinium bromide##STR38##

A 300 mg amount of 9-acetoxyellipticine, 762 mg of methyl(tri-O-acetyl-α-D-glucopyranosyl bromide)uronate, and 339 mg of cadmiumcarbonate were suspended in 30 ml of nitromethane and the suspension washeated under reflux for 15 minutes. The precipitate was removed byfiltration. The resultant solution was subjected to silicagel columnchromatography (silicagel: 600 ml) and was eluted with 8%methanol-chloroform solvent. The product was then subjected to gelfiltration chromatography (Sephadex LH-20 , 4.0 cmφ×38 cm) and waseluted with methanol.

Thus, 254 mg of the desired compound was obtained. The results are shownin Table 1.

EXAMPLE 53 Preparation of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-hydroxyellipticiniumbromide ##STR39##

A 500 mg amount of 9-hydroxyellipticine, 650 mg of cadmium carbonate,and 1.35 g of α-bromoaceto-L-rhamnose were suspended in 55 ml ofnitromethane and the resultant suspension was heated under reflux for 15minutes.

After cooling, the insoluble matter was removed by filtration and theresultant solution was concentrated to obtain 1.4 g of the residue.

The residue was subjected to silicagel column chromatography (elutionsolvent: 5% methanol-chloroform) to obtain 380 mg of the desiredcompound. The compound was futher purified by Sephadex LH-20 column.Thus, 235 mg of the purified desired compound was obtained.

The results are shown in Table 1.

EXAMPLE 54 Preparation of2-(2,3,5,-tri-O-benzoyl-β-D-xylofuranosyl)-9-hydroxyellipticiniumchloride ##STR40##

A 70 mg amount of 9-hydroxyellipticine, 70 mg of cadmium carbonate, and208 mg of 2,3,5-tri-O-benzoyl-α-D-xylofuranosyl chloride were suspendedin 7 ml of nitromethane and the mixture was heated under reflux for 10minutes. After removing the precipitate matter by filtration, theresidue obtained by concentration was subjected to silicagel columnchromatography (Kieselgel 60, 50 ml) and then, gel filtrationchromatography (Sephadex LH-20, 2.0 cmφ×18 cm). The desired compound wasobtained in an amount of 10.4 mg by elution with methanol.

The results are shown in Table 1.

Similarly,2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)-9-hydroxyellipticiniumchloride was obtained from 2,3,5-tri-O-benzoyl-α-L-xylofuranosylchloride.

EXAMPLES 55 TO 61

The following ellipticine derivatives were prepared in the same manneras in Examples 53 and 54. The results are shown in Table 1.

Example 55:2-(2,3,4-tri-O-benzoyl-α-D-arabinopyranosyl)-9-hydroyellipticiniumbromide.

Example 56: 2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-9-hydroxyellipticinium bromide.

Example 57:2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-9-hydroxyellipticiniumbromide.

Example 58:2-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-9-hydroxyellipticiniumbromide.

Example 59:2-(2,3,4-tri-O-benzoyl-α-L-arabinopyranosyl)-9-hydroxyellipticiniumbromide.

Example 60:2-(2,3,4-tri-O-acetyl-β-D-fucopyranosyl)-9-hydroxyellipticinium bromide.

Example 61:2-(2,3,4,-tri-O-acetyl-β-L-fucopyranosyl)-9-hydroxyellipticiniumbromide.

Example 62 Preparation of 2-β-D-galactopyranosyl-9-hydroxyellipticiniumbromide ##STR41##

A 199 mg amount of the tetraacetyl derivative obtained in Example 58 wasdissolved in 20 ml of methanol saturated with gaseous ammonia and wasallowed to stand at a temperature of 0° C. for 16 hours. After removingthe insoluble matter by filtration, methanol was distilled off in vacuo.The resultant residue was dissolved in 20 ml of methanol and 20 ml ofethyl acetate was added thereto. Thus, 23.4 mg of the desired compoundwas precipitated.

The results are shown in Table 1.

EXAMPLE 63 Preparation of 2-α-L-arabinofuranosyl-9-hydroxyellipticiniumbromide ##STR42##

A 238 mg amount of9-acetoxy-2-(2,3,5-tri-O-benzoyl-α-L-arabinofuranosyl)ellipticiniumbromide was dissolved in 25 ml of methanol saturated with gaseousammonia. The resultant solution was allowed to stand at a temperature of0° C. to 10° C. for 15 hours. After concentrating, the residue wasdissolved in methanol and ethyl acetate was added thereto. Thus, 107 mgof the desired compound was obtained by filtration.

The results are shown in Table 1.

EXAMPLE 64

Similarly in Example 63, 2-α-D-arabinofuranosyl-9-hydroxyellipticiniumbromide was obtained from the tri-O-benzoyl-α-D-arabinofuranosylcompound.

EXAMPLES 66 TO 70

The following ellipticinium derivatives were prepared in the same manneras in Examples 62 and 63. The results are shown in Table 1.

Example 66:

2-α-D-Mannopyranosyl-9-hydroxyellipticinium bromide.

2-α-L-Mannopyranosyl-9-hydroxyellipticinium bromide.

Example 67:

2-α-D-Talopyranosyl-9-hydroxyellipticinium bromide.

2-α-L-Talopyranosyl-9-hydroxyellipticinium bromide.

Example 68: 2-β-L-Galactopyranosyl-9-hydroxyellipticinium bromide.

Example 69:

2-β-D-Allopyranosyl-9-hydroxyellipticinium bromide.

2-β-L-Allopyranosyl-9-hydroxyellipticinium bromide.

Example 70: 2-β-L-Glucopyranosyl-9-hydroxyellipticinium bromide.

EXAMPLE 71 Preparation of 2-α-L-rhamnopyranosyl-9hydroxyellipticiniumbromide ##STR43##

A 80 mg amount of 2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-hydroxyellipticinium bromide was dissolved in 8ml of methanol saturated with gaseous ammonia. The resultant solutionwas allowed to stand in a refrigerator for 15 hours. Afterconcentrating, the resultant concentrate was precipitated withmethanolethyl acetate. Thus, 50 mg 80% yield) of the desired compoundwas obtained.

The results are shown in Table 1.

EXAMPLE 72 Preparation of2-(2-deoxy-β-D-ribofuranosyl)-9-hydroxyellipticinium chloride ##STR44##

A 92 mg amount of the compound obtained in Example 32 was dissolved in9.2 ml of methanol saturated with gaseous ammonia. The resultantsolution was allowed to stand at a temperature of 0° C. to 4° C.overnight. After distilling off the solvent in vacuo, the resultantresidue was dissolved in a small amount of methanol and, then wasprecipitated with ethyl acetate. Thus, 42 mg of the desired compound wasobtained in the form of red powder.

The results are shown in Table 1.

EXAMPLE 73 TO 76

The following ellipticine derivatives were prepared in the same manneras in Examples 71 and 72. The results are shown in Table 1.

Example 73: 2-(5- deoxy-β-D-ribofuranosyl)-9-hydroxyellipticiniumchloride.

Example 74: 2-(5-deoxy-α-L-arabinofuranosyl)-9-hydroxyellipticiniumchloride.

Example 75: 2-β-D-fucopyranosyl-9-hydroxyellipticinium bromide.

Example 76: 2-β-L-fucopyranosyl-9-hydroxyellipticinium bromide.

EXAMPLE 77 Preparation of 2-β-D-xylofuranosyl-9-hydroxyellipticiniumchloride ##STR45##

A 275 mg amount of9-acetoxy-2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)ellipticiniumchloride was dissolved in 30 ml of methanol saturated with gaseousammonia. The resultant solution was allowed to stand at room temperaturefor 15 hours. After concentrating, the resultant residue was dissolvedin a small amount of hot methanol and was precipitated with ethylacetate. Thus, 142 mg (89% yield) of the desired compound was obtained.Similarly, when 2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl) ellipticiniumchloride as used, 2-β-L-xylofuranosyl-9-hydroxyellipticinium chloridewas obtained.

The results are shown in Table 1.

EXAMPLE 78

2-β-D-xylofuranosyl-9-hydroxyellipticinium bromide was obtained in thesame manner as in Example 77.

EXAMPLE 79 Preparation of 2-β-D-erythrofuranosyl-9-hydroxyellipticiniumchloride ##STR46##

A 118 mg amount of the compound obtained in Example 29 was dissolved in15 ml of methanol saturated with gaseous ammonia. The resultant solutionwas allowed to stand at a temperature of 0° C. to 5° C. for 12 hours.After distilling off the solvent in vacuo, the resultant residue wasdissolved in methanol while heating and was precipitated with ethylacetate. Thus, 61 mg (84% yield) of the desired compound was obtained inthe form of reddish orange powder. The results are shown in Table 1.

At the same time, 7 mg of 2-α-D-erythrofuranosyl-9-hydroxyellipticiniumchloride was obtained. This α-compound was identified by the NMRspectrum of the 1-position of the sugar.

δ6.45 ppm, d, J=6.5 Hz.

The other signals of NMR spectrum, IR spectrum, and Mass spectrum werethe same as those of the β-compound.

Similarly, 2-β-L-erythrofuranosyl-9-hydroxyellipticinium chloride wasobtained from9-acetoxy-2-(2,3-di-O-benzoyl-β-L-erythrofuranosyl)ellipticiniumchloride.

EXAMPLE 80 Preparation of 2-β-L-ribopyranosyl-9-hydroxyellipticiniumbromide ##STR47##

A 110 mg amount of9-acetoxy-2-(2,3,4-tri-O-acetyl-β-L-ribopyranosyl)ellipticinium bromidewas allowed to stand in 15 ml of methanol saturated with gaseous ammoniaovernight in a refrigerator. The powder was precipitated withmethanol-ethyl acetate. Thus, 71 mg of the desired compound wasobtained.

The results are shown in Table 1.

EXAMPLE 81

2-β-D-ribopyranosyl-9-hydroxyellipticinium bromide was prepared in thesame manner as in Example 80.

The results are shown in Table 1.

EXAMPLE 82 Preparation of 2-β-L-ribofuranosyl-9-hydroxyellipticiniumbromide ##STR48##

A 370 mg amount of the compound obtained in Example 37 was dissolved in50 ml of methanol saturated with gaseous ammonia. The resultant solutionwas allowed to stand at a temperature of 0° C. to 5° C. for 15 hours.After concentrating, 170 mg of the desired compound was obtained in theform of red powder by using methanol-ethyl acetate.

The results are shown in Table 1.

EXAMPLE 83

2-β-D-ribofuranosyl-9-hydroxyellipticinium bromide was obtained in thesame manner as in Example 82.

The results are shown in Table 1.

EXAMPLE 84 Preparation of 2-α-D-arabinopyranosyl-9-hydroxyellipticiniumbromide ##STR49##

A 239 mg amount of2-(2,3,4-tri-O-benzoyl-α-D-arabinopyranosyl)-9-hydroxyellipticiniumbromide was allowed to stand in 23 ml of methanol saturated with gaseousammonia to obtain 119 mg of the desired compound in the same manner asmentioned above.

The results are shown in Table 1.

EXAMPLE 85

2-α-L-arabinopyranosyl-9-hydroxyellipticinium bromide was prepared inthe same manner as in Example 84.

EXAMPLE 86 Preparation of 2-α-D-lyxofuranosyl-9-hydroxyellipticiniumchloride ##STR50##

A 225 mg amount of the compound prepared in Example 34 was allowed tostand in 30 ml of methanol saturated with gaseous ammonia at atemperature of 0° C. to 10° C. for 15 hours. The solvent was removed invacuo and the resultant residue was dissolved in a small amount ofmethanol. From this solution, powder was precipitated with ethyl acetate(about 200 ml in total).

Thus, 112 mg of the desired compound in the form of reddish orangepowder. The results are shown in Table 1.

At the same time, 19 mg of 2-β-D-lyxofuranosyl-9-hydroxyellipticiniumchloride having the following formula was obtained: ##STR51##

The NMR spectrum of the hydrogen atom of β-form in the 1-position of thesugar was as follows:

δ6.42 ppm, doublet, J=6.5 Hz.

EXAMPLE 87

2-α-L-lyxofuranosyl-9-hydroxyellipticinium chloride was prepared from9-acetoxy-2-(2,3,5-tri-O-benzoyl-L-lyxofuranosyl)ellipticinium chlorideα-form/β-form=6/1 in the same manner as in Example 86.

EXAMPLE 88 Preparation of 2-α-L-lyxopyranosyl-9-hydroxyellipticiniumchloride ##STR52##

A 169 mg amount of9-acetoxy-2-(2,3,4-tri-O-acetyl-α-L-lyxopyranosyl)ellipticinium chloridewas treated with 17 ml of methanol saturated with gaseous ammonia in thesame manner as mentioned above. Thus, 88 mg of the desired compound wasobtained.

The results are shown in Table 1.

EXAMPLE 89

2-α-D-lyxopyranosyl-9-hydroxyellipticinium chloride was prepared in thesame manner as in Example 88.

The results are shown in Table 1.

EXAMPLE 90 Preparation of2-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-9-hydroxyellipticiniumchloride ##STR53##

A 198 mg amount of9-acetoxy-2-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)ellipticiniumchloride was dissolved in 24 ml methanol saturated with gaseous ammoniaand, then, the solution was allowed to stand at a temperature of 0° C.to 5° C. for 15 hours. Thus, 107 mg (72% yield) of the desired compoundwas obtained.

The results are shown in Table 1.

EXAMPLE 91

2-(2-acetamido-2-deoxy-β-D-galactopyranosyl)-9-hydroxyellipticiniumchloride was prepared in the same manner as in Example 90.

The results are shown in Table 1.

EXAMPLE 92 Preparation of2-β-D-glucuronamidopyranosyl-9-hydroxyellipticinium bromide ##STR54##

A 100 mg amount of 9-acetoxy-2-(methyl2,3,4-tri-O-acetyl-β-D-glucuronopyranosyl)ellipticinium bromide wasdissolved in 10 ml of methanol saturated with gaseous ammonia and, then,the solution was allowed to stand at a temperature of 0° C. to 5° C. for15 hours. The residue was treated with methanol-ethyl acetate. Thus, 65mg of the desired compound was obtained.

The results are shown in Table 1.

EXAMPLE 93 Preparation of 2-D-xylopyranosyl-9-hydroxyellipticiniumbromide ##STR55##

A 163 mg amount of the compound obtained in Example 40 was treated with20 ml of methanol saturated with gaseous ammonia in the same manner asmentioned above. Thus, 79 mg of the desired compound (1',2'-trans-isomerand 1',2'-cis-isomer) was obtained.

The proportion ratio of the isomers was determined in the following twomethods.

(1) Ratio determined by high pressure liquid chromatography

Column: Radial pack C-18 (available from Water's Co.).

Mobile phase:

(A) 100 mM ammonium acetate-30 mM Acetic acid.

(B) Methanol.

(C) Acetonitrile: A:B:C=2:0.4:0.6.

Flow rate: 3 ml/min.

Detection: 318 nm UV meter.

    ______________________________________                                        Product        Retention time (min)                                                                         %                                               ______________________________________                                        Main product   3.74           74.6                                            Another product                                                                              5.13           25.2                                            ______________________________________                                    

(2) Ratio determined by integrated value of NMR spectrum of the1-position of the sugar (360 MHz, DMSO-d₆)

Main product (1',2'-trans or β-form) δ:5.80 ppm, d, J=9 Hz.

Another product (1',2'-cis or α-form) δ:6.34 ppm, s Ratio of1',2'-trans/1',2'-cis=2.5/1.

The data in Table 1 represent the values of the main product in NMRspectrum and the values of the mixture in the other items.

The NMR spectrum of the α-isomer was as follows:

3.92 (1H,brs), 5.42 (1H,brs), 5.61 (1H,brs), 5.88 (1H,d) 6.34(1H,s,1'-H), 7.54 (1H,d,J=9 Hz), 8.44 (1H,d,J=7.5 Hz) 9.99 (1H,s).

EXAMPLE 94 Preparation of 2-L-xylopyranosyl-9-hydroxyellipticiniumbromide ##STR56##

The desired compound was prepared from the compound obtained in Example41 in the same manner as in Example 93.

This compound also had two isomers on the 1-position of the sugar.

(1) Ratio of the isomers by HPLC

    ______________________________________                                                                      Retention                                       Product              Ratio    time (min)                                      ______________________________________                                        Main product (1',2'-trans or β-form)                                                          84.2     3.73                                            Another product (1',2'-cis or α-form)                                                        15.6     5.14                                            ______________________________________                                    

(2) Ratio of the isomers by NMR spectrum (360 MHz, DMSO-d₆, H in1-position of the sugar)

    ______________________________________                                        Product                 Ratio                                                 ______________________________________                                        Main product (δ: 5.79 ppm, d, J = 9.0 Hz)                                                       6.8                                                   Another product (δ: 6.34 ppm, s)                                                                1                                                     ______________________________________                                    

The data in Table 1 represent the values of the main product in NMRspectrum and the values of the mixture in the other items.

EXAMPLE 95 Preparation of 2-α-L-rhamnopyranosyl-9-hydroxyellipticiniumacetate ##STR57##

A 190 mg amount of 2-α-L-rhamnopyranosyl-9-hydroxyellipticinium bromidewas dissolved in 40 ml of water and the resultant aqueous solution waspassed through ion-exchange column (BIO-RAD, AG1-X8, acetate type, 1.5cmφ×15 cm). The column was eluted with water. After concentrating, theresultant residue was treated with methanol-ethyl acetate to precipitatethe powder. By filtration, 156 mg of the desired compound was obtained.

The results are shown in Table 1.

EXAMPLE 96 Preparation of 2-β-D-arabinofuranosyl-9-hydroxyellipticiniumacetate ##STR58##

A 76 mg amount of 2-β-D-arabinofuranosyl-9-hydroxyellipticinium bromidewas dissolved in water and the resultant aqueous solution was passedthrough ion-exchange column (BIO-RAD, AG1-X8, acetate type, 1.2 cmφ×11cm).

Thus, 58 mg of the desired compound was obtained. The results are shownin Table 1.

Similarly, 2-β-L-arabinofuranosyl-9-hydroxyellipticinium acetate wasprepared from 2-β-L-arabinofuranosyl-9-hydroxyellipticinium bromide.

EXAMPLES 97 to 104

The following ellipticine derivatives were prepared in the same manneras in Examples 95 and 96. The results are shown in Table 1.

Example 97: 2-(5-Deoxy-β-L-arabinofuranosyl)-9-hydroxyellipticiniumacetate.

Example 98:

2-β-D-Ribopyranosyl-9-hydroxyellipticinium acetate.

2-β-L-Ribopyranosyl-9-hydroxyellipticinium acetate.

Example 99:

2-α-D-Lyxofuranosyl-9-hydroxyellipticinium acetate.

2-α-L-Lyxofuranosyl-9-hydroxyellipticinium acetate.

Example 100:

2-β-L-Fucopyranosyl-9-hydroxyellipticinium acetate.

2-β-D-Fucopyranosyl-9-hydroxyellipticinium acetate.

Example 101:

2-α-D-Arabinopyranosyl-9-hydroxyellipticinium acetate.

2-α-L-Arabinopyranosyl-9-hydroxyellipticinium acetate.

Example 102:

2-β-L-Galactopyranosyl-9-hydroxyellipticinium acetate.

2-β-D-Galactopyranosyl-9-hydroxyellipticinium acetate.

Example 103:

2-α-D-Lyxopyranosyl-9-hydroxyellipticinium acetate.

2-α-L-Lyxopyranosyl-9-hydroxyellipticinium acetate.

Example 104:

2-β-D-Xylofuranosyl-9-hydroxyellipticinium acetate.

EXAMPLE 105 Preparation of2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-9-hydroxyellipticiniumacetate ##STR59##

A 257 mg amount of2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-9-hydroxyellipticiniumbromide (Example 57) was treated in ion-exchange column (BIO-RAD,AG1-X8, acetate type).

Thus, 214 mg of the desired compound was obtained.

EXAMPLE 106 Preparation of 2-L-xylopyranosyl-9-hydroxyellipticiniumacetate ##STR60##

A 18 mg amount of the desired compound was obtained by treating 32.5 mgof the compound obtained in Example 94. The results are shown in Table1.

The resultant compound had two isomers on the hydrogen atom in the1-position of the sugar. The ratio was 6.8:1.

The NMR spectrum of the main product (i.e., 1',2'-trans or β-form) wasas follows (360 MHz, DMSO-d₆, δ2.50 ppm, CD₂ HSOCD₃ as internalstandard):

1.66(3H,s), 2.69(3H,s), 3.08(3H,s), 3.68(3H,m), 4.06(1H,m) 5.67(1H,d,J=9Hz,1'-H), 7.00(1H,dd,J=2,9 Hz) 7.50(1H, d,J=9 Hz), 7.75(1H, d,J=2 Hz),8.11(1H,d,J=7.5 Hz) 8.27(1H, d.J=7.5 Hz), 9.64(1H,s).

2-D-xylopyranosyl-9-hydroxyellipticinium acetate was prepared from thecompound obtained in Example 93 by the ion-exchange treatment in thesame manner as mentioned above.

This compound had two isomers on the hydrogen atom in the 1-position ofthe sugar. The NMR spectrum of the main product (i.e., 1',2'-trans orβ-form) was identical to that of2-β-L-xylopyranosyl-9-hydroxyellipticinium acetate. The ratio of the twoisomers was also identical to that of Example 93.

EXAMPLE 107 Preparation of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-hydroxyellipticiniumbromide ##STR61##

A 50 mg amount of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-methoxyellipticiniumbromide (Example 25) was dissolved in 2.5 ml of dry methylene chlorideand, then, 20 drops of iodotrimethylsilane were added thereto. Themixture was allowed to stand for 3 days to form a precipitate. Theresultant precipitate was recovered by filtration. Thus, 42 mg (86%yield) of the desired compound was obtained.

The physical properties are shown in Example 53.

EXAMPLE 108 Preparation of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)-9-hydroxyellipticiniumchloride ##STR62##

A 50 mg amount of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)-9-methoxyellipticiniumchloride (Example 27) was dissolved in 2.5 ml of dry methylene chlorideand, then, 20 drops of iodotrimethylsilane were added thereto. Themixture was allowed to stand for 3 days to form precipitate. Theresultant precipitate was recovered by filtration. Thus, 44 mg (90%yield) of the desired compound was obtained.

The physical properties are shown in Example 54.

EXAMPLE 109 Preparation of2-(5-deoxy-β-L-arabinofuranosyl)-9-hydroxyellipticinium chloride##STR63##

A 289 mg amount of9-acetoxy-2-(2,3-di-O-benzyl-5-deoxy-β-L-arabinofuranosyl)ellipticiniumchloride was dissolved in 19 ml of dry methylene chloride and, then, 109drops of iodotrimethylsilane were added thereto. The mixture was allowedto stand at a temperature of 0° C. to 5° C. for 15 hours. Theprecipitate thus formed was recovered and was then dissolved in 40 ml ofmethanol saturated with gaseous ammonia. The solution was allowed tostand at a temperature of 0° C. to 5° C. for 4 hours. Afterconcentrating, the desired compound was obtained in the form of powderby treating the residue with methanol-ethyl acetate. The yield was 150mg (81%).

The results are shown in Table 1.

EXAMPLES AND 110 AND 111

The following ellipticine derivatives were prepared in the same manneras in Example 109. The results are shown in Table 1.

Example 110: 2-β-D-Arabinofuranosyl-9-hydroxyellipticinium bromide.

Example 111: 2-β-L-Arabinofuranosyl-9-hydroxyellipticinium bromide

EXAMPLE 112 Preparation of 2-β-D-glucopyranosyl-9-hydroxyellipticiniumacetate ##STR64##

A 63.7 g amount of the tetraacetyl derivative obtained in Example 105was dissolved in 8.5 ml of methanol saturated with gaseous ammonia. Thesolution was allowed to stand at a temperature of 0° C. overnight. Theresultant dark red precipitate was removed by filtration and thefiltrate was concentrated to obtain the powder product.

The powder product was then subjected to Sephadex LH-20 column (solvent:methanol). Thus, 20 mg of the purified product was obtained. Thephysical properties are shown in Table 1.

    TABLE 1      Example No. 1 2 3 4       R      ##STR65##      ##STR66##      ##STR67##      ##STR68##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous orange powder Amorphous orange powder Specific rotatory     -18° (C = 0.17, EtOH) +53° (C = 0.12, EtOH) -180°     (C = 0.19, MeOH -150° (C = 0.24, MeOH) power [α].sub.D     Infrared absorption 1750, 1590, 1430, 1370, 1240 3300, 1635, 1590, 1420,     1235 1729, 1606, 1450, 1425, 1261, 3238, 1598, 1425, 1384, 1253, (KBr,     cm.sup.-1)   1113, 711 1105, 753 Ultraviolet 244 (ε21000) 244     (ε20000) 230 (ε49000) 204 (ε19000) absorption     250 (ε20000) 251 (ε19000) 245 (ε22000) 245     (ε22000) (λ.sub.max.sup.EtOH, nm) 286 (ε21000)     313 (ε62000) 313 (ε63000) 313 (ε63000)  317     (ε58000) Mass spectrum 577 409 619 379 (SIMS, m/z) [C.sub.31     H.sub.33 O.sub.9 N.sub.2 ].sup.+ [C.sub.23 H.sub.25 O.sub.5 N.sub.2 ]     .sup.+ [C.sub.43 H.sub.35 O.sub.7 N.sub.2 ].sup.+ [C.sub.22 H.sub.23     O.sub.4 N.sub.2 ].sup.+ Proton NMR 1.81, 1.98, 2.01, 2.30, (each 2.83,     (3H,s) 3.70 (3H,m) 3.89 2.90 (3H,s) 4.98 (2H,m) 5.18 2.90 (3H,s) 3.80,     3.93, (each (DMSO-d.sub.6, δ in ppm, 3H,s) 2.91 (3H,s) 3.38 (3H,s)     (3H,m) 4.88 (1H,t) 4.98, 5.24, (1H,q) 6.12 (1H,t) 6.19 (1H, 1H) 4.26     (2H,brs), 4.37 (1H, CD.sub.2 HSOCD.sub.3 proton 4.25 (2H,m) 4.76 (1H,t)     5.56 5.62 (each 1H,d) 5.87 (1H,d,J t) 7.05 (1H,d,J=5Hz, 1'-H) brs) 5.57,     5.65, 6.00 (each chemical shift (δ (3H,m) 6.45 (1H,d,J=8.5Hz,     =9Hz,1'-H) 7.41 (1H,dt,J= 8.48 (1H,d,J=8Hz) 8.54 (1H, 1H,brs) 6.30     (1H,d,J=5Hz,1'-H) 2.50) was used as 1'-H) 7.46 (1H,ddd,J=8, 7, 2.6Hz)     7.67 (2H,m) 8.43 (1H,d, d,J=7.5Hz) 8.77 (1H,d,J=7.5Hz) 7.43 (1H,dd,J=8,7H     z) 7.71 (2H, internal standard, 2Hz) 7.74 (2H,m) 8.54 (1H,d, J=7.5Hz)     8.53 (2H,m) 10.07 10.25 (1H,s) 12.44 (1H,brs) m) 8.51 (1H,d,J=8Hz) 8.58     (1H), Intensity of NMR J=8Hz) 8.58 (2H,s) 10.14 (1H, (1H,s) 12.28     (1H,brs) (360MHz) (300MHz) d,J=7.5Hz) 8.71 (1H,d,J=7.5Hz) magnetic field     was s) 12.46 (1H,brs) (360MHz)   10.32 (1H,s) 12.15 (1H,brs) indicated     in each    (300MHz) compound) Elementary analysis C.sub.31 H.sub.33     N.sub.2 O.sub.9 Br C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br C.sub.43     H.sub.35 N.sub.2 O.sub.7 Br C.sub.22 H.sub.23 N.sub.2 O.sub.4 Br     Molecular formula Calc. (C, H, N) % 56.62, 5.06, 4.26 56.45, 5.15, 5.73     66.93, 4.57, 3.63 57.52, 5.05, 6.10 Found (C, H, N) % 56.69, 5.24, 4.06     56.18, 5.32, 5.61 67.15, 4.60, 3.52 57.24, 4.96, 5.85       Example No. 5 6 7 8       R      ##STR69##      ##STR70##      ##STR71##      ##STR72##       X.sup.- Br.sup.- CH.sub.3      CO.sub.2.sup.- Br.sup.- Br.sup.-               Crystalline form     Amorphous orange powder Amorphous orange powder Amorphous orange powder     Amorphous orange powder Specific rotatory -63° (C = 0.21, EtOH)     +43° (C = 0.24, EtOH) -4.7° (C = 0.17, MeOH -170°     (C = 0.15, H.sub.2 O) power [α].sub.D Infrared absorption 1750,     1600, 1420, 1380, 1370 3200, 1640, 1600, 1580, 1420 1754, 1647, 1598,     1434, 1376, 3345, 1639, 1598, 1434, 1253, (KBr, cm.sup.-1) 1240 1240     1253, 1220 1163, 1105 Ultraviolet 229 (ε18000) 207 (ε2000     0) 230 (ε17000) 206 (ε20000) absorption 243 (ε240     00) 244 (ε23000) 245 (ε23000) 244 (ε22000)     (λ.sub.max.sup.EtOH, nm) 252 (ε23000) 251 (ε23000)      252 (ε22000) 251 (ε22000)  286 (ε24000) 313     (ε70000) 286 (ε23000) 313 (ε61000)  317 (.epsilon     .61000)  316 (ε62000) Mass spectrum 577 409 519 393 (SIMS, m/z)     [C.sub.31 H.sub.33 O.sub.9 N.sub.2 ].sup.+ [C.sub.23 H.sub.25 O.sub.5     N.sub.2 ].sup.+ [C.sub.29 H.sub.31 O.sub.7 N.sub.2 ].sup.+ [C.sub.23     H.sub.25 O.sub.4 N.sub.2 ].sup.+ Proton NMR 1.81, 2.02, 2.07, 2.10,     (each 1.70, (3H,s) 2.80 (3H,m) 3.23 1.26 (3H,d,J=6.5Hz) 1.80 1.31     (3H,d,J=6Hz), 2.88 (3H,s) (DMSO-d.sub.6, δ in ppm, 3H,s) 2.90     (3H,s) 3.42 (3H,s) (3H,s) 5.87 (1H,d,J=8.5Hz, 2.00, 2.31 (each 3H,s)     2.88 3.67 (2H,m) 3.87 (1H,m) 4.05 CD.sub.2 HSOCD.sub.3 proton 4.27     (2H,m) 4.45 (1H,m) 5.59 1'-H) 7.37 (1H,t,J=7Hz) 7.63 (3H,s) 3.38 (3H,s)     4.57 (1H,q) (1H,m) 4.97, 5.22, 5.57 (each chemical shift (δ (2H,m)     5.94 (1H,t) 6.43 (1H,d, (1H,t,J=7Hz) 7.69 (1H,d,J=7Hz) 5.39 (1H,d,) 5.50     (2H,m) 6.44 1H,d) 5.83 (1H,d,J=9Hz,1'-H) 2.50) was used as J=9Hz,1'-H)     7.46 (1H,dt,J=2, 8.34 (1H,d,J=7.5Hz) 8.38 (1H, (1H,d,J=8Hz,1'-H)7.46     (1H, 7.43 (1H,ddd,J=8,6,2Hz) 7.72 internal standard, 6Hz) 7.73 (2H,m)     8.54 (2H,m) d,J=7.5Hz) 8.53 (1H,d,J=7Hz) ddd,J=8,7,2Hz) 7.74 (2H,m)     (2H,m) 8.50 (1H,d,J=8Hz) 8.56 Intensity of NMR 8.73 (1H,d,J=7.5Hz) 10.21     (1H, 9.98 (1H,s) (360MHz) 8.53 (1H,d,J=8Hz) 8.57 (2H,s) (2H,s) 10.10     (1H,s) 12.32 (1H magnetic field was s) 12.42 (1H,brs) (360MHz)  10.15     (1H,s) 12.46 (1H,brs) brs) (300MHz) indicated in each   (300MHz)     compound) Elementary analysis C.sub.31 H.sub.33 N.sub.2 O.sub.9 Br     C.sub.25 H.sub.28 N.sub.2 O.sub.7 C.sub.29 H.sub.31 N.sub.2 O.sub.7 Br     C.sub.23 H.sub.25 N.sub.2 O.sub.4 Br Molecular formula Calc. (C, H, N) %     56.62, 5.06, 4.26 64.09, 6.02, 5.98 58.10, 5.21, 4.67 58.35, 5.32, 5.92     Found (C, H, N) % 56.49, 5.21, 3.99 64.05, 6.33, 6.21 58.32, 5.03, 4.51     58.09, 5.18, 6.03       Example No. 9 10 11 12       R      ##STR73##      ##STR74##      ##STR75##      ##STR76##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous orange powder Amorphous orange powder Specific rotatory     -6.2° (C =  0.21, MeOH) +180° (C = 0.11, H.sub.2 O)     -13° (C = 0.19, EtOH) -20° (C =      0.11, EtOH) power [α].sub.D Infrared absorption 1754, 1647, 1598,     1434, 1376 3345, 1639, 1598, 1434, 1253 1750, 1600, 1430, 1370, 1240,     3200, 1640, 1600, 1420, 1240, (KBr, cm.sup.-1) 1235, 1220 1163, 1105     Ultraviolet Same as in compound 7 Same as in compound 8 230 (ε160     00) 204 (ε19000) absorption   244 (ε22000) 244 (ε     23000) (λ.sub.max.sup.EtOH, nm)   252 (ε21000) 250     (ε23000)    286 (ε21000) 312 (ε74000)    316     (ε61000) Mass spectrum 519 393 519 393 (SIMS, m/z) [C.sub.29     H.sub.31 O.sub.7 N.sub.2 ].sup.+ [C.sub.23 H.sub.25 O.sub.4 N.sub.2     ].sup.+ [C.sub.29 H.sub.31 O.sub.7 N.sub.2 ].sup.+ [C.sub.23 H.sub.25     O.sub.4 N.sub.2 ].sup.+ Proton NMR Same as in compound 7 Same as in     compound 8 1.54 (3H,d,J=6.5Hz) 1.86, 1.54 (3H,d,J=6Hz) 2.90 (3H,s)     (DMSO-d.sub.6, δ in ppm,   2.18, 2.24 (each 3H,s) 2.90 3.37 (3H,s)     3.71, 4.00, 4.11, CD.sub.2 HSOCD.sub.3 proton   (3H,s) 3.43 (3H,s) 4.53     (1H,m) 4.33 (each 1H,m) 5.41, 5.47, chemical shift (δ   4.98     (1H,t) 5.52 (1H,t) 5.81 5.65 (each 1H,d) 6.26 (1H,d, 2.50) was used as     (1H,dd,J=3, 8.5Hz) 6.69 (1H,d, J=9Hz,1'-H) 7.43 (1H,ddd,J=8, internal     standard,   J=8.5Hz,1'-H) 7.46 (1H,ddd, 7,2Hz) 7.73 (2H,m) 8.50 (1H,d,     Intensity of NMR   J=8,7,2Hz) 7.73 (2H,m) 8.55 J=8Hz) 8.54 (1H,d,J=7.5Hz)      8.63 magnetic field was   (2H,m) 8.66 (1H,d,J=7.5Hz) (1H,d,J=7.5Hz)     10.14 (1H,s) indicated in each   10.17 (1H,s) 12.44 (1H,brs) 12.34     (1H,brs) compound)   (360MHz) (360MHz) Elementary analysis C.sub.29     H.sub.31 N.sub.2 O.sub.7 Br C.sub.23 H.sub.25 N.sub.2 O.sub.4 Br     C.sub.29 H.sub.31 N.sub.2 O.sub.7 Br C.sub.23 H.sub.25 N.sub.2 O.sub.4     Br Molecular formula Calc. (C, H, N) % 58.10, 5.21, 4.67 58.35, 5.32,     5.92 58.10, 5.21, 4.67 58.35, 5.32, 5.92 Found (C, H, N) % 58.12, 5.25,     4.81 58.25, 5.41, 5.72 57.89, 5.33, 4.70 58.41, 5.49, 5.85       Example No. 13 13 14 14       R      ##STR77##      ##STR78##      ##STR79##      ##STR80##       X.sup.- Cl.sup.- Cl.sup.- Cl.sup.- Cl       Crystalline form Amorphous yellow powder Amorphous yellow powder     Amorphous yellow powder Amorphous yellow powder Specific rotatory     -76° (C = 0.23, MeOH) +80° (C = 0.19, MeOH) -39° (C     = 0.19, 1(v/v %) +40° (C = 0.21, 1% CF.sub.3      COOH/ power [α].sub.D   CF.sub.3 CO.sub.2 H/H.sub.2 O H.sub.2 O)     Infrared absorption 1730, 1720, 1650, 1600, 1460, Same as in the left     3200, 1640, 1595, 1575, 1420, Same as in the left (KBr, cm.sup.-1) 1430,     1250, 1100, 710  1240, 1090, 750 Ultraviolet 232 (ε55000)  207     (ε21000) absorption 286 (ε25000)  244 (ε24000)     (λ.sub.max.sup.EtOH, nm) 316 (ε70000)  311 (ε(7400     0) Mass spectrum 691  379 (SIMS, m/z) [C.sub.43 H.sub.35 N.sub.2 O.sub.7     ].sup.+  [C.sub.32 H.sub.23 N.sub.2 O.sub.4 ].sup.+ Proton NMR 2.90     (3H,s) 4.96 (1H,dd)  2.83 (3H,s) 3.27 (3H,s) 3.98 (DMSO-d.sub.6, δ     in ppm, 5.14 (1H,dd) 5.42 (1H,  (2H,m) 4.16 (1H,s) 4.35 (1H,s) CD.sub.2     HSOCD.sub.3 proton quintet) 6.12 (2H,m)  4.50 (1H,m) 5.12 (1H,t)     chemical shift (δ 7.05 (1H,s,1'-H)  5.74 (1H,brs) 6.50 1H,brs)     2.50) was used as 7.33-8.25 (18H,m) 8.47  6.35 (1H,s,1'-H) 7.38 internal     standard, (1H,d,J=8Hz) 8.56 (1H,d, (1H,dt,J=1.5,6.0Hz) 7.66 Intensity of     NMR J=7.5Hz) 8.80 (1H,d,J=7.5Hz)  (2H,m) 8.42 (1H,md,J=8.0Hz, magnetic     field was 10.16 (1H,s) 12.49 (1H,brs)  10-H) 8.48 (1H,d,J=7.5Hz) 8.66     indicated in each   (1H,d,J=7.5Hz) 10.15 (1H,s) compound)   12.28     (1H,brs) Elementary analysis -- -- -- -- Molecular formula Calc. (C, H,     N) % Found (C, H, N) %       Example No. 15 16 17 18       R      ##STR81##      ##STR82##      ##STR83##      ##STR84##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous yellow powder Amorphous yellow powder     Amorphous red powder Amorphous red powder Specific rotary +5.7°     (C = 0.23, MeOH) +45° (C = 0.11, MeOH) -180° (C = 0.29,     MeOH) -180° (C = 0.083, H.sub.2 O) power [α].sub.D Infrared     absorption 1754, 1639, 1598, 1491, 1434, 3386, 1647, 1598, 1483, 1417,     1729, 1647, 1598, 1483, 1270, 3394, 1638, 1598, 1483, 1425, (KBr,     cm.sup.-) 1376, 1229 1311, 1261, 1220, 1097 1106, 712 1302, 1261, 1220,     1106 Ultraviolet 226 (ε16000) 226 (ε14000) 230 (ε     49000) 226 (ε16000) absorption 249 (ε24000) 255 (.epsilon     .22000) 269 (ε25000) 254 (ε24000) (λ.sub.max.sup.E     tOH, nm) 256 (ε24000) 265 (ε21000) 324 (ε50000)     265 (ε24000)  268 (ε23000) 280 (ε20000)  280     (ε21000)  326 (ε51000) 321 (ε49000)  321     (ε54000) Mass spectrum 607 439 721 409 (SIMS, m/z) [C.sub.32     H.sub.35 O.sub.10 N.sub.2 ].sup.+ [C.sub.24 H.sub.27 O.sub.6 N.sub.2     ].sup.+ [C.sub.44 H.sub.37 O.sub.8 N.sub.2 ].sup.+ [C.sub.23 H.sub.25     O.sub.5 N.sub.2 ].sup.+ Proton NMR 1.81, 1.98, 2.01, 2.30, (each 2.87     (3H,s) 3.95 (3H,s) 4.85 2.86 (3H,s) 3.27 (3H,s) 3.94 2.86 (3H,s) 3.95     (2H,s) 4.26 (DMSO-d.sub.6, δ in ppm, 3H,s) 2.87 (3H,s) 3.96 (3H,s)     (1H,t) 4.97, 5.25, 5.62 (each (3H,s) 4.98 (2H,m) 5.18 (1H,m) (2H,m) 4.35     (1H,brs) 5.50, CD.sub.2 HSOCD.sub.3 proton 4.24 (2H,m) 4.75 (1H,t) 5.56     1H,d) 5.83 (1H,d,J=9Hz,1'-H) 6.11 (1H,t) 6.19 (1H,t) 7.05 5.86 (each     1H,d) 5.63 (1H,t) chemical shift (δ (3H,m) 6.44 (1H,d,J=8.5H,1'-H)     7.35 (1H,dd,J=2,9Hz) 7.65 (1H, (1H,d,J=5Hz,1'-H) 7.34 (1H,dd, 6.29     (1H,d,J=5Hz,1'-H) 7.33 2.50) was used as 7.37 (1H,dd,J=2,9Hz) 7.67 (1H,     d,J=9Hz) 7.97 (1H,d,J=2Hz) J=2,9Hz) 8.49 (1H,d,J=7.5Hz) (1H,dd,J=2,9Hz)     7.63 (1H,d, internal standard d,J=9Hz) 7.98 (1H,d,J=2Hz) 8.54 (2H,q)     10.11 (1H,s) 8.73 (1H,d,J=7.5Hz) 10.23 (1H, J=9Hz) 7.94 (1H,d,J=2Hz)     8.54 Intensity of NMR 8.54 (2H,s) 10.13 (1H,s) 12.25 (300MHz) s) 12.28     (1H,brs) (1H,d,J=7.5Hz) 8.67 (1H,d, magnetic field was (1H,brs)     (300MHz) J=7.5Hz) 10.28 (1H,s) 12.14 indicated in each (300MHz)     (1H,brs) compound)    (300MHz) Elementary analysis C.sub.32 H.sub.35     N.sub.2 O.sub.10 Br C.sub.24 H.sub.27 N.sub.2 O.sub.6 Br C.sub.44     H.sub.37 N.sub.2 O.sub.8 Br C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br     Molecular formula Calc. (C, H, N) % 55.90, 5.13, 4.07 55.50, 5.24, 5.39     65.92, 4.65, 3.49 56.45, 5.15, 5.73 Found (C, H, N) % 55.85, 5.25, 4.18     55.46, 5.29, 5.18 66.13, 4.59, 3.52 56.36, 5.17, 5.65       Example No. 19 20 21 22       R      ##STR85##      ##STR86##      ##STR87##      ##STR88##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous red powder Amorphous red powder Amorphous     red powder Amorphous red powder Specific rotatory -68° (C = 0.20,     MeOH) +44° (C = 0.16, MeOH) +22° (C =       0.25, MeOH +46° (C = 0.19, MeOH) power [α].sub.D Infrared     absorption 1754, 1647, 1598, 1491, 1425 3361, 1639, 1598, 1483, 1425     1754, 1647, 1598, 1491, 1425, 3402, 1639, 1598, 1483, 1417, (KBr,     cm.sup.-1) 1376, 1220 1311, 1270, 1204, 1114 1376, 1220 1311, 1261,     1220, 1155 Ultraviolet 226 (ε15000) 226 (ε15000) 227     (ε15000) 227 (ε15000) absorption 268 (ε22000)     266 (ε23000) 256 (ε23000) 266 (ε24000) (λ.     sub.max.sup.EtOH, nm) 249 (ε23000) 321 (ε52000) 326     (ε49000) 321 (ε52000)  325 (ε48000) 255 (.epsilon     .23000) 250 (ε23000) 255 (ε23000)   279 (ε21000)     267 (ε23000) 279 (ε21000) Mass spectrum 607 439 549 423     (SIMS, m/z) [C.sub.32 H.sub.35 O.sub.10 N.sub.2 ].sup.+ [C.sub.24     H.sub.27 O.sub.6 N.sub.2 ].sup.+ [C.sub.30 H.sub.33 O.sub.8 N.sub.2     ].sup.+ [C.sub.24 H.sub.27 O.sub.5 N.sub.2 ].sup.+ Proton NMR 1.79,     2.02, 2.06, 2.09 (each 2.84 (3H,s) 3.31 (3H,s) 3.95 1.26 (3H,d,J=6.5Hz)     1.80, 1.30 (3H,d,J=6.5Hz) 2.85 (3H, (DMSO-d.sub.6, δ in ppm, 3H,s)     2.85 (3H,s) 3.34 (3H,s) (3H,s) 4.82 (1H,t) 5.39, 5.52, 2.00, 2.30 (each     3H,s) 2.86 s) 3.32 (3H,s) 3.66 (2H,m) CD.sub.2 HSOCD.sub.3 proton 3.96     (3H,s) 4.27 (2H,m) 4.44 5.72 (each 1H,d) 5.90 (1H,d, (3H,s) 3.33 (3H,s)     3.96 (3H,s) 3.88 (1H,m) 4.04 (1H,q) 3.96 chemical shift (δ (1H,m)     5.58 (2H,m) 5.94 (1H,t) J=9Hz,1'-H) 7.33 (1H,dd,J=2, 4.55 (1H,q) 5.39     (1H,d) 5.48 (3H,s) 4.97, 5.21, 5.56 (each 2.50) was used as 6.41     (1H,d,J=9Hz,1'-H) 7.35 9Hz) 7.62 (1H,d,J=9Hz) 7.92 (2H,m) 6.42 (1H,d,J=8.     5Hz,1'-H) 1H,d) 5.82 (1H,d,J=8.5Hz,1'-H) internal standard, (1H,dd,J=2,9H     z) 7.66 (1H,d, (1H,brs) 8.46 (1H,d,J=7.5Hz) 7.36 (1H,dd,J=2,9Hz) 7.66     (1H, 7.34 (1H,dd,J=2,9Hz) 7.64 (1H, Intensity of NMR J=9Hz) 7.98     (1H,brs) 8.50 (1H, 8.59 (1H,d,J=7.5Hz) 10.07 (1H, d,J=9Hz) 7.97 (1H,d,J=2     Hz) d,J=9Hz) 7.95 (1H,d,J=2Hz) magnetic field was d,J=7.5Hz) 8.70     (1H,d,J=7.5Hz) s) 12.16 (1H,brs) 8.52 (2H,s) 10.13 (1H,s) 12.33 8.53     (2H,s) 10.08 (1H,s) 12.14 indicated in each 10.18 (1H,s) 12.30 (1H,brs)     (300MHz) (1H,brs) (1H,brs) compound) (300MHz)  (300MHz) (300MHz)     Elementary analysis C.sub.37 H.sub.35 N.sub.2 O.sub.10 Br C.sub.24     H.sub.27 N.sub.2 O.sub.6 Br C.sub.30 H.sub.33 N.sub.2 O.sub.8 Br     C.sub.24 H.sub.27 N.sub.2 O.sub.5 Br Molecular formula Calc. (C, H, N) %     55.90, 5.13, 4.07 55.50, 5.24, 5.39 57.24, 5.28, 4.45 57.26, 5.41, 5.57     Found (C, H, N) % 56.11, 4.98, 4.26 55.48, 5.29, 5.61 57.09, 5.12, 4.60     57.51, 5.24, 5.65       Example No. 23 24 25 26       R      ##STR89##      ##STR90##      ##STR91##      ##STR92##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous red powder Amorphous red powder Amorphous     red powder Amorphous red powder Specific rotatory -19° (C = 0.15,     MeOH) -50° (C = 0.21, MeOH) - 47° (C = 0.24, MeOH)     -7.5° (C = 0.20, MeOH) power [α].sub.D Infrared absorption     1754, 1647, 1598, 1491, 1425 3402, 1639, 1598, 1483, 1417 1754, 1639,     1598, 1483, 1425, 3361, 1647, 1598, 1483, 1417 (KBr, cm.sup.-1) 1376,     1220 1311, 1261, 1220, 1155 1376, 1220 1311, 1261, 1212, 1138 Ultraviolet      Same as in compound 21 Same as in compound 22 226 (ε16000) 249     (ε23000) 226 (ε16000) 255 (ε24000) absorbtion     256 (ε23000) 267 (ε23000) 266 (ε24000) 279     (ε22000) (λ.sub.max.sup.EtOH, nm)   324 (ε49000)     321 (ε55000) Mass spectrum 549 423 549 423 (SIMS, m/z) [C.sub.30     H.sub.33 O.sub.8 N.sub.2 ].sup.+ [C.sub.24 H.sub.27 O.sub.5 N.sub.2     ].sup.+ [C.sub.30 H.sub.33 O.sub.8 N.sub.2 ].sup.+ [C.sub.24 H.sub.27     O.sub.5 N.sub.2 ].sup.+ Proton NMR Same as in compound 21 Same as in     compound 22 1.53 (3H,d,J=7Hz) 1.86, 2.18, 1.53 (3H,d,J=7Hz) 2.87 (3H,s)     (DMSOd.sub.6, δ in ppm,   2.23 (each 3H,s) 2.87 (3H,s) 3.70, 3.98,     4.08, 4.32 (each CD.sub.2 HSOCD.sub.3 proton   3.96 (3H,s) 4.50 (1H,m)     4.98 1H,m) 3.96 (3H,s) 5.40, 5.47, chemical shift (δ   (1H,t) 5.51     (1H,t) 5.80 (1H,dd, 5.67 (each 1H,d) 6.24 (1H,d, 2.50) was used as     J=3,8Hz) 6.66 (1H,d,J=8Hz, J=9Hz,1'-H) 7.35 (1H,dd, internal standard,     1'-H) 7.36 (1H,dd,J=2,9Hz) J=2,9Hz) 7.66 (1H,d,J=9Hz) 7.98 Intensity of     NMR   7.66 (1H,d,J=9Hz) 7.99 (1H,brs) (1H,d,J=2Hz) 8.53 (1H,d, magnetic     field was   8.51 (1H,d,J=7.5Hz) 8.62 (1H,d, J=7.5Hz) 8.59 (1H,d,J=7.5Hz)     indicated in each   J=7.5Hz) 10.13 (1H,s) 12.15 10.14 (1H,s) (300MHz)     compound)   (1H,brs) (300MHz) Elementary analysis C.sub.30 H.sub. 33     N.sub.2 O.sub.8 Br C.sub.24 H.sub.27 N.sub.2 O.sub.5 Br C.sub.30     H.sub.33 N.sub.2 O.sub.8 Br C.sub.24 H.sub.27 N.sub.2 O.sub.5 Br     Molecular formula Calc. (C, H, N) % 57.24, 5.28, 4.45 57.26, 5.41, 5.57     57.24, 5.28, 4.45 57.26, 5.41, 5.57 Found (C, H, N) % 57.28, 5.02, 4.63     57.31, 5.27, 5.57 57.100, 5.28, 4.49 57.15, 5.26, 5.68       Example No. 27 27 28 28       R      ##STR93##      ##STR94##      ##STR95##      ##STR96##       X.sup.- Cl.sup.- Cl.sup.- Cl.sup.- Cl.sup.-       Crystalline form Amorphous red powder Amorphous red powder Amorphous     orange powder Amorphous orange powder Specific rotatory - 90° (C     = 0.30, MeOH) +90° (C = 0.35, MeOH) -130° (C = 0.15, DMSO)     +120° (C = 0.12, DMSO) power [α].sub.D Infrared absorption     1720, 1640, 1590, 1480, 1250 Same as in the left 3250, 1640, 1595, 1480,     1420, Same as in the left (KBr, cm.sup.-1) 1090, 1060, 1020, 800, 700     1380, 1300, 1250, 1220, 1090,    1030, 970, 805 Ultraviolet 231 (.epsilon     .58000)  208 (ε19000) absorption 268 (ε30000)  226     (ε14000) (λ.sub.max.sup.EtOH, nm) 324 (ε60000)     256 (ε21000)    266 (ε21000)    279 (ε20000)     320 (ε48000) Mass spectrum 721  409 (SIMS, m/z) [C.sub.44     H.sub.37 N.sub.2 O.sub.8 ].sup.+  [C.sub.23 H.sub.25 N.sub.2 O.sub.5     ].sup.+ Proton NMR 2.86 (3H,s) 3.94 (3H,s) 4.95  2.80 (3H,s) 3.25 (3H,s)     3.92 (DMSOd.sub.6, δ in ppm, (1H,dd) 5.14 (1H,dd) 5.42 (1H,     (3H,s) 3.97 (2H,m) 4.16 (1H, CD.sub.2 HSOCD.sub.3 proton quintet) 6.10     (2H,brs)  brs) 4.34 (1H,s) 4.49 (1H,m) chemical shift (δ 7.03     (1H,s,1'-H) 7.32-8.25 (18H,m)  5.10 (1H,t) 5.73 (1H,brs) 2.50) was used     as 8.53 (1H,d,J=7.5Hz) 8.76 (1H,  6.38 (1H,brs) internal standard,     2,J=7.5Hz) 10.16 (1H,s) 12.35  6.33 (1H,s,1'-H) 7.28 Intensity of NMR     (1H,brs)  (1H,dd,J=2.9Hz) 7.57 (1H,d, magnetic field was   J=9Hz) 7.83     (1H,d,J=2Hz) 8.43 indicated in each   (1H,d,J=7.5Hz) 8.62 (1H,d,     compound)   J=7.5Hz) 10.12 (1H,s) 12.12    (1H,brs) Elementary analysis     Molecular formula Calc. (C, H, N) % Found (C, H, N) %       Example No. 29 29 30 31      ##STR97##      ##STR98##      ##STR99##      ##STR100##      R (D-Ery) (L-Ery) (D-5d Rib) (L-5d Ara)       X.sup.- Cl Cl Cl Cl       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous orange powder Amorphous orange powder Specific rotatory     -180° (C = 0.13) +170° (C = 0.21) -130° (C = 0.20)     -290° (C = 0.15) power [α].sub.D Infrared absorption 1730,     1600, 1470, 1420, 1280, 1730, 1600, 1470, 1420, 1100, 1730, 1600, 1470,     1280, 1100, 1730, 1640, 1600, 1480, 1460, (KBr, cm.sup.-1) 1100, 710     710, 1280 720 1420, 1260, 1210, 1100, 1060,     1020, 920, 810, 720     Ultraviolet 231 (ε36000) 231 (ε36000) 231 (ε38000     ) 235 (ε42000) absorption 284 (ε21000) 284 (ε2100     0) 285 (ε23000) 285 (ε22000) (λ.sub.max.sup.EtOH,     nm) 315 (ε63000) 315 (ε63000) 315 (ε68000) 315     (ε66000) Mass spectrum 615 615 629 629 (SIMS, m/z) [C.sub.37     H.sub.31 N.sub.2 O.sub.7 ].sup.+ [C.sub.37 H.sub.31 N.sub.2 O.sub.7     ].sup.+ [C.sub.38 H.sub.33 N.sub.2 O.sub.7l ].sup.+ [C.sub.38 H.sub.33     N.sub. 2 O.sub.7 ].sup.+ Proton NMR 2.36 (3H,s) 2.91 (3H,s) 4.60 same as     in the left 1.76 (3H,d,J=6.5Hz) 2.37 (3H, 1.68 (3H,d,J=6.5Hz) 2.37 (3H,     (DMSOd.sub.6, δ in ppm, (1H,d,J=10.5Hz) 5.21 (1H,dd,  s) 2.93     (3H,s) 4.83 (1H,m) s) 2.73 (3H,s) 3.30 (3H,s) CD.sub.2 HSOCD.sub.3     proton J=4.0,10.5Hz) 6.07 (1H,t,  5.75 (1H,dd) 6.15 (1H,t) 5.44 (1H,m)     5.60 (1H,s) 6.13 chemical shift (δ J=3.5Hz) 6.27 (1H,dd,J=3.5,4.0Hz     )  6.94 (1H,d,J=5Hz,1'-H) 7.44-8.03 (1H,s) 7.14 (1H,s,1'-H) 2.50) was     used as 7.01 (1H,d,J=6.5Hz,1'-H)  (12H,m) 8.26 (1H,d,J=2Hz) 8.62     7.19-8.17 (12H,m) 8.24 (1H,d internal standard, 7.24 (1H,m) 7.42 (m)     (1H,d,J=7.5Hz) 8.78 (1H,d, J=2Hz) 8.24 (1H,d,J=2Hz) 8.62 Intensity of     NMR 7.61 (m) 7.75 (m) 7.85 (2H,d)  7.5Hz) 10.27 (1H,s) 12.55 (1H,     (1H,d,J=7.5Hz) 8.75 (1H,d, magnetic field was 8.08 (2H,d) 8.23 (1H,d,     brs) J=7.5Hz) 10.07 (1H,s) 12.45 indicated in each J=2.5Hz) 8.60     (1H,d,J=7.5Hz)   (1H,brs) compound 8.83 (1H,d,J=7.5Hz) 10.28 (1H,  s)     12.55 (1H,brs) Elementary analysis -- -- -- -- Molecular formula Calc.     (C, H, N) % Found (C, H, N) %       Example No. 32 33 35 35      ##STR101##      ##STR102##      ##STR103##      ##STR104##      R (D-2d Rib) (L-5d Ara) (D-Xyl) (L-Xyl)       X.sup.- Cl Cl Cl Cl       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous orange powder Amorphous orange powder Specific rotatory     -240° (C = 0.2) +11° (C = 0.30) -75° (C = 0.19)     +80° (C = 0.14) power [α].sub.D Infrared absorption 1720,     1610, 1470, 1270, 1180, 1760, 1600, 1480, 1420, 1370, 1730, 1600, 1470,     1450, 1420, 1730, 1600, 1470, 1450, 1420, (KBr, cm.sup.-1) 1100, 750     1200, 1090, 920, 820, 740, 700 1260, 1100, 1070, 1020, 710 1260, 1100,     1070, 1020, 710 Ultraviolet 243 (ε46000) 204 (ε34000)     233 (ε52000) 233 (ε55000) absorption 284 (ε20000)      252 (ε24000) 282 (ε22000) 276 (ε24000) (λ     .sub.max.sup.EtOH, nm) 314 (ε59000) 314 (ε69000) 315     (ε67000) 284 (ε24000)     316 (ε72000) Mass     spectrum 657 601 749 749 (SIMS, m/z) [C.sub.40 H.sub.37 N.sub.2 O.sub.7     ].sup.+ [C.sub.38 H.sub.37 N.sub.2 O.sub.5 ].sup.+ [C.sub.45 H.sub.37     N.sub.2 O.sub.9 ].sup.+ [C.sub.45 H.sub.37 N.sub.2 O.sub.9 ].sup.+     Proton NMR 2.19 (3H,s) 2.36 (3H,s) 2.44 1.60 (3H,d,J=6.5Hz) 2.37 (3H,     2.37 (3H,s) 2.90 (3H,s) 3.30 2.37 (3H,s) 2.90 (3H,s) 3.30 (DMSOd.sub.6,     δ in ppm, (3H,s) 2.86 (3H,s) 3.05 (1H,m) s) 2.88 (3H,s) 3.23     (3H,s) (3H,s) 4.95 (1H,dd) 5.14 (1H, (3H,s) 4.95 (1H,dd) 5.14 (1H,     CD.sub.2 HSOCD.sub.3 proton 3.26 (3H,s) 4.75 (1H,dd) 4.85 4.22 (2H,m)     4.50 (2H,m) 4.68 dd) 5.43 (1H, quintet) 6.11 dd) 5.43 (1H,quintet) 6.11     chemical shift (δ (1H,dd) 4.96 (1H,m) 5.78 (1H,m) (3H,m) 6.80     (3H,m) 7.00 (3H,m) (1H,d) 6.14 (1H,s) dd) 5.43 (1H,quintet) 6.11 2.50)     was used as 6.98 (1H,t,J=6.5Hz,1'-H) 7.32-7.44 (4H,m) 7.46 (1H,dd, 7.04     (1H,s1'-H) (1H,d) 6.14 (1H,s) internal standard, 7.10 (2H,d,J=8Hz) 7.43     (2H,d, J=2,9Hz) 7.73 (1H,d,J=9Hz) 7.33-8.25 (18H,m) 8.56 7.04 (1H,S,1'-H)      Intensity of NMR J=8Hz) 7.68 (2H,d,J=8Hz) 8.00 8.23 (1H,d,J=2Hz) 8.48     (2H,s) (1H,d,J=7.5Hz) 8.81 (1H,d, (1H,d,J=7.5Hz) 8.81 (1H,d, magnetic     field was (2H,d,J=8Hz) 7.47 (1H,dd, 10.03 (1H,s) 12.51 (1H,brs) J=7.5Hz)     10.20 (1H,s) 12.58 J=7.5Hz) 10.20 (1H,s) 12.58 indicated in each     J=2.9Hz) 7.73 (1H,d,J=9Hz)  (1H,brs) (1H,brs) compound 8.25 (1H,d,J=2Hz)     8.46 (1H,d,  J=7.5Hz) 8.59 (1H,d,J=7.5Hz)  10.08 (1H,s) 12.39 (1H,brs)     Elementary analysis   C.sub.45 H.sub.37 N.sub.2 O.sub.9 Cl.3H.sub.2 O     C.sub.45 H.sub.37 N.sub.2 O.sub.9 Cl.3H.sub.2 O Molecular formula Calc.     (C, H, N) %   64.40, 5.16, 3.34 64.40, 5.16, 3.34 Found (C, H, N) %     64.38, 4.92, 3.53 64.69, 4.90, 3.62       Example No. 36 36 37 38      ##STR105##      ##STR106##      ##STR107##      ##STR108##      R (D-Ara) (L-Ara) (L-Rib) (D-Xyl)       X.sup.- Br Br Br Br       Crystalline form Amorphous red powder Amorphous orange powder Amorphous      orange powder Amorphous orange powder Specific rotatory +180° (C     = 0.11) -190° (C = 0.11) +200° (C = 0.22) -86° (C =     0.10) power [α].sub.D Infrared absorption 1730, 1600, 1480, 1460,     1420, 1730, 1600, 1480, 1460, 1420, 1720, 1640, 1590, 1440, 1720, 1600,     1470, 1450, 1420, (KBr, cm.sup.-1) 1280, 1210, 1100, 1080, 1030, 1280,     1210, 1100, 1080, 1030, 1260, 1100, 700 1260, 1200, 1100, 1060, 1020,     720 720  710 Ultraviolet 233 (ε54000) 232 (ε52000) 231     (ε50000) 233 (ε56000) absorption 276 (ε23000)     281 (ε22000) 276 (ε23000) 276 (ε23000) (λ.     sub.max.sup.EtOH, nm) 284 (ε23000) 315 (ε67000) 284     (ε23000) 284 (ε23000)  316 (ε70000)  316     (ε67000) 316 (ε71000) Mass spectrum 749 749 749 749     (SIMS, m/z) [C.sub.45 H.sub.37 N.sub.2 O.sub.9 ].sup.+ [C.sub.45     H.sub.37 N.sub.2 O.sub.9 ].sup.+ [C.sub.45 H.sub.37 N.sub.2 O.sub.9     ].sup.+ [C.sub.45 H.sub.37 N.sub.2 O.sub.9 ].sup.+ Proton NMR 2.36     (3H,s) 2.94 (3H,s) 4.86 Same of in the left 2.36 (3H,s) 2.90 (3H,s) 3.26     2.37 (3H,s) 2.91 (3H,s) 4.95 (DMSOd.sub.6, δ in ppm, (2H,m) 5.74     (1H,m) 6.02 (1H,t)  (3H,s) 4.97 (2H,t) 5.18 (1H,q) (1H,dd) 5.13 (1H,dd)     5.42 (1H, CD.sub.2 HSOOCD.sub.3 proton 6.24 (1H,t)  6.12 (1H,t) 6.20     (1H,t) quintet) 6.10 (1H,d) 6.13 (1H,s) chemical shift (δ 7.20     (1H,d,J=1.5Hz,1'-H)  7.04 (1H,d,J=5Hz,1'-H) 7.02 (1H,s,1'-H) 7.33-8.25     2.50) was used as 7.30-8.15 (17H,  7.44-8.05 (18H,m) 8.57 (1H,d,J=7.5Hz)     internal standard, m) 8.26 (1H,d,J=2Hz) 8.63 (1H,  (17H,m) 8.23 (1H,d,J=2     Hz) 8.54 8.81 (1H,d,J=7.5Hz) 10.18 (1H, Intensity of NMR d,J=7.5Hz) 8.84     (1H,d,J=7.5Hz)  (1H,d,J=7.5Hz) 8.76 (1H,d, s) 12.50 (1H,brs) magnetic     field was 10.16 (1H,s) 12.44 (1H,brs)  J=7.54Hz) 10.25 (1H,s) 12.43     (1H,brs) indicated in each   (1H,brs) compound) Elementary analysis --     -- -- -- Molecular formula Calc. (C, H, N) % Found (C, H, N) %       Example No. 39 39 40 41      ##STR109##      ##STR110##      ##STR111##      ##STR112##      R (D-Ara) (L-Ara) (D-Xyl) (L-Xyl)       X.sup.- Br Br Br Br       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous red powder Amorphous red powder Specific rotatory +38°     (C = 0.16) -40° (C = 0.24) -87° (C = 0.15) +71° (C     = 0.09) power [α].sub.D Infrared absorption 1760, 1600, 1470,     1410, 1360, 1760, 1600, 1470, 1410, 1360, 1760, 1600, 1470, 1420, 1380,     (KBr, cm.sup.-1) 1200, 1190, 910, 730, 690 1200, 1190, 910, 730, 690     1220, 1060, 810 1220, 1060, 810 Ultraviolet 252 (ε25000) 252     (ε25000) 246 (ε25000) 250 (ε18000) absorption     315 (ε71000) 315 (ε71000) 252 (ε25000) 286     (ε15000) (λ.sub.max.sup.EtOH, nm)   285 (ε21000)     316 (ε46000)    316 (ε66000) Mass spectrum 707 707 563     563 (SIMS, m/z) [C.sub.45 H.sub.43 N.sub.2 O.sub.6 ].sup.+ [C.sub.45     H.sub.43 N.sub.2 O.sub.6 ].sup.+ [C.sub.30 H.sub.31 N.sub.2 O.sub.9     ].sup.+ [C.sub.30 H.sub.31 N.sub. 2 O.sub.9 ].sup.+ Proton NMR 2.37     (3H,s) 2.85 (3H,s) 3.21 same as in the left 1.78, 2.04, 2.08 (each 3H,s)     Same as in the left (DMSOd.sub.6, δ in ppm, (3H,s) 3.90 (2H,m)     4.34-4.80  2.36 (3H,s) 2.89 (3H,s) 3.88 (1',2'-Trans form) CD.sub.2     HSOCD.sub.3 proton (10H,m) 6.85 (3H,m) 7.03 (3H,  (1H,m) 4.37 (1H,m)     5.52 (2H,m) chemical shift (δ m) 7.32-7.44 (9H,m) 7.47 (1H,  5.92     (1H,t) 2.50) was used as dd,J=2,9Hz) 7.73 (1H,d,J=9Hz)  6.31 (1H,d,J=9Hz,     1'-H) internal standard, 8.23 (1H,d,J=2H) 8.25 (1H,d,  7.48 (1H,dd,J=2,9H     z) Intensity of NMR J=7.5Hz) 8.61 (1H,d,J=7.5Hz)  7.74 (1H,d,J=9Hz) 8.29     (1H,d, magnetic field was 10.06 (1H,s) 12.36 (1H,brs)  J=2Hz) 8.56     (1H,d,J=7.5Hz) 8.72 indicated in each   (1H,d,J=7.5Hz) 10.23 (1H,s)     compound)   12.55 (1H,brs)    'HNMR exhibits the value of 1',     2'-trans form. Elementary analysis C.sub.45 H.sub.43 N.sub.2 O.sub.6     Br.1/2H.sub.2 O C.sub.45 H.sub.43 N.sub.2 O.sub.6 Br.1/2H.sub.2 O     Molecular formula Calc. (C, H, N) % 67.83, 5.57, 3.52 67.83, 5.57, 3.52     Found (C, H, N)% 67.71, 5.63, 3.24 67.90, 5.50, 3.51       Example No. 42 42 43 43      ##STR113##      ##STR114##      ##STR115##      ##STR116##      R (D-Ara) (L-Ara) (D-Rib) (L-Rib)       X.sup.- Br Br Br Br       Crystalline form Amorphous red powder Amorphous red powder Amorphous     orange powder Amorphous orange powder Specific rotatory -48° (C =     0.16) +39° (C = 0.20) +7.0° (C = 0.20) -9.2° (C =     0.12) power [α].sub.D Infrared absorption 1750, 1640, 1600, 1480,     1420, 1750, 1640, 1600, 1480, 1420, 1760, 1640, 1600, 1480, 1420, 1760,     1640, 1600, 1480, 1420, (KBr, cm.sup.-1) 1370, 1220, 1060, 940, 810,     1370, 1220, 1060, 940, 810 1380, 1220, 1100, 1040, 920, 1380, 1220,     1100, 1040, 920,    820 820 Ultraviolet 247 (ε15000) 253     (ε22000) 250 (ε35000) 246 (ε26000) absorption     285 (ε13000) 386 (ε19000) 285 (ε29000) 253     (ε26000) (λ.sub.max.sup.EtOH, nm) 316 (ε39000)     317 (ε57000) 316 (ε81000) 285 (ε22000)     316     (ε68000) Mass spectrum 563 563 563 563 (SIMS, m/z) [C.sub.30     H.sub.31 N.sub.2 O.sub.9 ]+ [C.sub.30 H.sub.31 N.sub.2 O.sub.9 ]+     [C.sub.30 H.sub.31 N.sub.2 O.sub.9 ]+ [C.sub.30 H.sub.31 N.sub.2 O.sub.9     ]+ Proton NMR 1.80, 2.00, 2,27 (each 3H,s) Same as in the left 1.76,     2.06, 2.31 (each 3H,s) Same as in the left (DMSO-d.sub.6 , δ in     ppm, 2.37 (3H,s) 2.89 (3H,s) 3.35  2.37 (3H,s) 2.90 (3H,s) 3.32 CD.sub.2     HSOCD.sub.3 proton (3H,s) 4.33 (2H,s) 5.43 (1H,s)  (3H,s) 4.07 (1H,t)     4.26 (1H,q) chemical shift (δ 5.51 (2H,portion AB in ABX,  5.54     (1H,m) 5.79 (1H,t) 5.93 (1H,dd) 2.50) was used as J.sub.2',3'      =10Hz,J.sub.1',3' =4Hz)  6.47 (1H,d,J=9Hz,1'-H) internal standard, 6.35     (1H, portion X in ABX,  7.47 (1H,dd,J=2,9Hx) 7.74 (1H, Intensity of NMR     J.sub.1',2' =8Hz,1'-H) 7.48 (1H,dd,  d,J=9Hz) 8.28 (1H,d,J=2Hz) magnetic     field was J=2,9Hz) 7.74 (1H,d,J=9Hz)  8.58 (1H,d,J=7.5Hz) 8.78 (1H,     indicated in each 8.29 (1H,d,J=2Hz) 8.57 (2H,  d,J=7.5Hz) 10.28 (1H,s)     12.50 compound) AB quartet) 10.16 (1H,s) 12.48  (1H,brs)  (1H,brs)     Elementary analysis -- -- C.sub.30 H.sub.31 N.sub.2 O.sub.9      Br.2.5H.sub.2 O C.sub.30 H.sub.31 N.sub.2 O.sub.9 Br.2.5H.sub.2 O     Molecular formula Calc. (C, H, N) %   52.33, 5.27, 4.07 52.33, 5.27,     4.07 Found (C, H, N) %   52.36, 5.15, 4.00 52.27, 5.03, 4.17       Example No. 44 44 45 45      ##STR117##      ##STR118##      ##STR119##      ##STR120##      R (D-Lyx) (L-Lyx) (D-Man) (L-Man)       X.sup.- Cl Cl Br Br       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous red powder Amorphous red powder Specific rotatory -110°     (C = 0.13) +100° (C = 0.30) +24° (C = 0.16) -24° (C     = 0.11) power [α].sub.D Infrared absorption 1760, 1640, 1600,     1480, 1420, 1760, 1640, 1600, 1480, 1420, 1740, 1640, 1600, 1480, 1420,     1740, 1640, 1600, 1480, 1420, (KBr, cm.sup.-1) 1380, 1220, 1060, 920,     820, 1380, 1220, 1060, 920, 820 1370, 1220, 1120, 1050, 820 1370, 1220,     1120, 1050, 820, Ultraviolet 206 (ε16000) 209 (ε19000)     252 (ε23000) 246 (ε24000) absorption 251 (ε22000)      253 (ε23000) 286 (ε20000) 252 (ε24000) (λ     .sub.max.sup.EtOH, nm) 285 (ε19000) 286 (ε20000) 316     (ε 62000) 286 (ε21000)  316 (ε57000) 316     (ε62000)  316 (ε61000) Mass spectrum 563 563 635 635     (SIMS, m/z) [C.sub.30 H.sub.31 N.sub.2 O.sub.9 ]+ [C.sub.30 H.sub.31     N.sub.2 O.sub.9 ]+ [C.sub.33 H.sub.35 N.sub.2 O.sub.11 ]+ [C.sub.33     H.sub.35 N.sub.2 O.sub.11 ]+ Proton NMR 1.77, 2.27, 2.29 (each 3H,s)     Same as in the left 1.86, 2.05, 2.20, 2.24 (each Same as in the left     (DMSO-d.sub.6 , δ in ppm, 2.37 (3H,s) 2.91 (3H,s) 3.37  3H,s) 2.37     (3H,s) 2.92 (3H,s) CD.sub.2 HSOCD.sub.3 proton (3H,s) 4.26, 4.33, (each     1H,  3.38 (3H,s) 4.48 (1H,dd) 4.64 chemical shift (δ AB quartet,J=1     3Hz) 5.05  (2H,m) 5.18 (1H,t) 5.55 2.50) was used as (1H,d) 5.55 (2H,m)     (1H,t) 5.83 (1H,dd) internal standard, 6.56 (1H,d,J=9Hz, 1'-H)  6.74     (1H,d,J=8.5Hz,1'-H) Intensity of NMR 7.48 (1H,dd,J=2,9Hz)  7.47 (1H,dd,     magnetic field was 7.74 (1H,d,J=9Hz) 8.28 (1H,d,  J=2,9Hz) 7.74 (1H,d,J=9     Hz) indicated in each J=2Hz) 8.54 (1H,d,J=7.5Hz)  8.29 (1H,d,J=2Hz) 8.57     (1H,d, compound) 8.66 (1H,d,J=7.5Hz) 10.27  J=7.5Hz) 8.66 (1H,d,J=7.5Hz)      (1H,s) 12.55 (1H,brs)  10.15 (1H,s) 12.42 (1H,brs) Elementary analysis     -- -- -- -- Molecular formula Calc. (C, H, N) % Found (C, H, N) %       Example No. 46 46 47 47      ##STR121##      ##STR122##      ##STR123##      ##STR124##      R (D-All) (L-All) (D-Tal) (L-Tal)       X.sup.- Br Br Br Br       Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous orange powder Amorphous orange powder Specific rotatory     -22° (C = 0.26) +20° (C = 0.19) +100° (C =  0.22)     -95° (C = 0.31) power [α].sub.D Infrared absorption 1760,     1640, 1600, 1480, 1420, 1760, 1640, 1600, 1480, 1420, 1750, 1640, 1600,     1480, 1380, 1750, 1640, 1600, 1480, 1380, (KBr, cm.sup.-1) 1370, 1220,     1040, 910, 820, 1370, 1220, 1040, 910, 820 1220, 1100, 1040, 920, 820     1220, 1100, 1040, 920, 820 Ultraviolet 206 (ε20000) 206 (.epsilon     .20000) 246 (ε28000) 246 (ε28000) absorption 246     (ε25000) 246 (ε25000) 252 (ε27000) 252 (ε     27000) (λ.sub.max.sup.EtOH, nm) 252 (ε25000) 252 (.epsilon     .25000) 286 (ε23000) 286 (ε23000)  286 (ε21000)     286 (ε21000) 316 (ε74000) 316 (ε74000)  316     (ε66000) 316 (ε66000) Mass spectrum 635 635 635 635     (SIMS, m/z) [C.sub.33 H.sub.35 N.sub.2 O.sub.11 ]+ [C.sub.33 H.sub.35     N.sub.2 O.sub.11 ]+ [C.sub.33 H.sub.35 N.sub.2 O.sub.11 ]+ [C.sub.33     H.sub.35 N.sub.2 O.sub.11 ]+ Proton NMR 1.79, 2.06, 2.08, 2.30 (each     Same as in the left 1.77, 2.02, 2.11, 2.29 (each Same as in the left     (DMSO-d.sub.6 , δ in ppm, 3H,s) 2.37 (3H,s) 2.90 (3H,s)  3H,s)     2.37 (3H,s) 2.90 (3H,s) CD.sub.2 HSOCD.sub.3 proton 3.35 (3H,s) 4.23     (1H,dd) 4.41  3.37 (3H,s) 4.47 (1H,d) 4.70 chemical shift (δ     (1H,dd) 4.51 (1H,m) 5.45 (1H,  (1H,t) 4.88 (1H,dd) 5.74 2.50) was used     as dd) 5.80 (1H,t) 5.93 (1H,dd)  (2H,m) 5.91 (1H,dd) internal standard,     6.59 (1H,d,J=9.5Hz,1'-H) 7.47  6.69 (1H,d,J=9Hz,1'-H) Intensity of NMR     (1H,dd,J=2,9Hz) 7.72 (1H,d,  7.47 (1H,dd,J=2, magnetic field was J=9Hz)     8.27 (1H,d,J=2Hz) 8.57  9Hz) 7.72 (1H,d,J=9Hz) 8.28 indicated in each     (1H,d,J=7.5Hz) 8.77 (1H,d,  (1H,d,J=2Hz) 8.62 (1H,d, compound) J=7.5Hz)     10.26 (1H,s) 12.48  J=7.5Hz) 8.82 (1H,d,J=7.5Hz)  (1H,brs)  10.29 (1H,s)     12.48 (1H,brs) Elementary analysis -- -- -- -- Molecular formula Calc.     (C, H, N) % Found (C, H, N) %       Example No. 48 49 50 51      ##STR125##      ##STR126##      ##STR127##      ##STR128##      R (L-Gal) (L-Glc) (D-Glc NAc) (D-Gal NAc)       X.sup.- Br Br Cl Cl       Crystalline form Amorphous orange powder Amorphous red powder Amorphous      orange powder Amorphous orange powder Specific rotatory +3.7° (C     = 0.30) +75° (C = 0.19) -110° (C = 0.19) -41° (C =     0.19) power [α].sub.D Infrared absorption 1760, 1640, 1600, 1480,     1420, 1760, 1640, 1600, 1480, 1420, 1760, 1600, 1480, 1420, 1370, 1750,     1660, 1600, 1470, 1420, (KBr, cm.sup.-1) 1380, 1220, 1060, 940 1390,     1220, 1040 1220, 1050, 940, 920, 820 1370, 1220, 910, 810 Ultraviolet     246 (ε27000) 246 (ε25000) 207 (ε18000) 208     (ε18000) absorption 253 (ε26000) 286 (ε21000)     253 (ε23000) 253 (ε24000) (λ .sub.max.sup.EtOH,     nm) 286 (ε23000) 317 (ε66000) 286 (ε20000) 285     (ε20000)  318 (ε67000)  317 (ε63000) 317     (ε65000) Mass spectrum 635 635 634 634 (SIMS, m/z) [C.sub.33     H.sub.35 N.sub.2 O.sub.11 ]+ [C.sub.33 H.sub.35 N.sub.2 O.sub.11 ]+     [C.sub.33 H.sub.36 N.sub.3 O.sub.10 ]+ [C.sub.33 H.sub.36 N.sub.3     O.sub.10 ]+ Proton NMR 1.80, 1.99, 2.01, 2.28 (each 1.79, 2.02, 2.06,     2.09 (each 1.50 (3H,s) 1.98, 2.06, 2.08 1.50 (3H,s) 1.96, 2.02, 2.27     (DMSO-d.sub.6 , δ in ppm, 3H,s) 2.37 (3H,s) 2.90 (3H,s) 3H,s) 2.37     (3H,s) 2.89 (3H,s) (each 3H,s) 2.37 (3H,s) 2.87 (each 3H,s) 2.37 (3H,s)     2.89 CD.sub.2 HSOCD.sub.3 proton 3.35 (3H,s) 4.25 (2H,m) 3.37 (3H,s)     4.26 (2H,m) 4.44 (3H,s) 3.34 (3H,s) 4.28 (2H.m) (3H,s) 4.25 (2H,m) 4.54     (1H,m) chemical shift (δ 4.76 (1H,m) 5.54 (3H,m) (1H,m) 5.58     (2H,m) 5.95 (1H,t) 4.33 (1H,m) 4.93 (1H,q, 4.65 (1H,t) 5.33 (1H,dd) 5.54     (1H,d) 2.50) was used as 6.46 (1H,d,J=9Hz,1'-H) 6.41 (1H,d,J=9Hz,1'-H)     7.48 J=9.5Hz) 5.35 (1H,t,J= 9.5Hz) 6.23 (1H,d,J=9.5Hz 1'-H) internal     standard, 7.47 (1H,dd,J=1.5, (1H,dd,J=2,9Hz) 7.74 (1H,d, 5.44 (1H,t,J=9.5     Hz) 7.47 (1H,dd,J=2,9Hz) Intensity of NMR 9Hz) 7.72 (1H,dd,1.5,9Hz) 8.27     J=9Hz) 8.28 (1H,d,J=2Hz) 8.55 6.26 (1H,d,J=9.5Hz,1'-H) 7.74 (1H,d,J=9Hz)     8.27 (1H,d, magnetic field was (1H,t,1.5Hz) 8.57 (2H,s) 10.16 (1H,d,J=7.5     Hz) 8.74 (1H,d, 7.46 (1H,dd, J=2Hz) 8.44 (1H,d,J=8Hz) 8.50 indicated in     each (1H,s) 12.55 (1H,brs) J=7.5Hz) 10.23 (1H,s) 12.52 J=2,9Hz) 7.73     (1H,d,J=9Hz) (1H,d,J=7.5Hz) 8.55 (1H,d, compound)  (1H,brs) 8.26     (1H,d,J=2Hz) 8.42 (1H,d, J=7.5Hz) 10.04 (1H,s) 12.45    J=9.5Hz) 8.53     (1H,d,J=7.5Hz) (1H,brs)    8.64 (1H,d,J=7.5Hz) 10.14 (1H,    s) 12.55     (1H,brs) Elementary analysis -- -- -- -- Molecular formula Calc. (C, H,     N) % Found (C, H, N) %       Example No. 52 53 54 54      ##STR129##      ##STR130##      ##STR131##      ##STR132##      R (D-Glc UA)       X.sup.- Br Br.sup.- Cl.sup.- Cl.sup.-       Crystalline form Amorphous red powder Amorphous red powder Amorphous     red powder Amorphous red powder Specific rotatory -79° (C = 0.09)     +59° (C = 0.11,EtOH) -120° (C = 0.13,MeOH) +120° (C     = 0.15, CH.sub.3 OH) power [α].sub.D Infrared absorption 1760,     1640, 1600, 1480, 1420, 3350, 3150, 1750, 1640, 1590, 3400, 3100, 1730,     1640, 1595, Same as in the left (KBr, cm.sup.-1) 1370, 1220, 1040 1475,     1425, 1380, 1370, 1220, 1585, 1470, 1450, 1425, 1260,    1090, 810, 700     Ultraviolet 206 (ε21000) 226 (ε15000) 231 (ε50000     ) absorption 246 (ε25000) 251 (ε22000) 271 (ε2700     0) (λ.sub.max.sup.EtOH, nm) 286 (ε21000) 269 (ε230     00) 326 (ε48000)  318 (ε64000) 326 (ε45000) Mass     spectrum 621 535 707 (SIMS, m/z) [C.sub.32 H.sub.33 N.sub.2 O.sub.11 ]+     [C.sub.29 H.sub.31 O.sub.8 N.sub.2 ]+ [C.sub.45 H.sub.35 N.sub.2 O.sub.8     ]+ Proton NMR 1.79, 2.04, 2.09 (each 3H,s) 1.55 (3H,d,J=7Hz) 1.85, 2.20,     2.85 (3H,s) 3.27 (3H,s) 4.96 (DMSO-d.sub.6 δ in ppm, 2.37 (3H,s)     2.88 (3H,s) 3.70 2.25 (each 3H,s) 2.86 (3H,s) (1H,dd) 5.12 (1H,dd) 5.40     (1H, CD.sub.2 HSOCD.sub.3 proton (3H,s) 4.90 (1H,d,J=9.5Hz) 3.35 (3H,s)     4.52 (1H,m) 4.98 quintet) 6.10 (2H,brs) chemical shift (δ 5.66     (1H,t,J=9.5Hz) 5.71 (1H, (1H,t) 5.50 (1H,t) 5.77 (1H, 7.01 (1H,s,1'-H)     2.50) was used as t,J=9.5Hz) 6.06 (1H,t,J=9.5Hz) dd,J=3,8.5Hz) 6.67     (1H,d, 7.20 (1H,dd,J=2, internal standard, 6.47 (1H,d,J=9.5Hz,1'-H) 7.47     J=8.5Hz,1'-H) 7.20 (1H,dd, 9Hz) 7.33-8.24 (17H,m) 8.51 Intensity of NMR     (1H,dd,J=2,9Hz) 7.74 (1H,d, J=2,9Hz) 7.56 (1H,d,J=9Hz) (1H,d,J=7.5Hz)     8.75 (1H,d, magnetic field was J=9Hz) 8.27 (1H,d,J=2Hz) 8.54 7.87     (1H,d,J= 2Hz) 8.48 (1H,d, J=7.5Hz) 9.54 (1H,s) 10.10 indicated in each     (1H,d,J=7.5Hz) 8.78 (1H,d, J=7.5Hz) 8.60 (1H,d,J=7.5Hz) (1H,s) 12.23     (1H,brs) compound) J=7.5Hz) 10.26 (1H,s) 12.55 9.50 (1H,s) 10.12 (1H,s)     12.23  (1H,brs) (1H,brs)   (360MHz) Elementary analysis -- C.sub.29     H.sub.31 N.sub.2 O.sub.8 Br -- -- Molecular formula Calc. (C, H, N) %     56.59, 5.08, 4.55 Found (C, H, N) %  56.41, 5.29, 4.37       Example No. 55 56 57 58       R      ##STR133##      ##STR134##      ##STR135##      ##STR136##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous red powder Amorphous red powder Amorphous     red powder Amorphous red powder Specific rotatory -99° (C = 0.15,     MeOH) -170° (C = 0.23, EtOH) -63° (C = 0.073, EtOH)     +13° (C = 0.10, MeOH) power [α].sub.D Infrared absorption     3400, 3100, 1725, 1640, 1600, 3400, 3100, 1725, 1640, 1595, 3350, 3100,     1750, 1640, 1585, 3435, 3238, 1745, 1655, 1598, (KBr, cm.sup.-1) 1590,     1475, 1450, 1430, 1250 1585, 1470, 1450, 1420, 1260 1470, 1425, 1365,     1215 1483, 1434, 1376, 1229 Ultraviolet 231 (ε51000) 231     (ε46000) 249 (ε26000) 226 (ε14000) absorption     271 (ε27000) 271 (ε20000) 255 (ε26000) 250     (ε21000) (λ.sub.max.sup. EtOH, nm) 328 (ε48000)     327 (ε46000) 261 (ε26000) 271 (ε22000)    270     (ε26000) 328 (ε42000)    328 (ε47000) Mass     spectrum 707 707 593 593 (SIMS, m/z) [C.sub.45 H.sub.35 N.sub.2 O.sub.8     ]+ [C.sub.45 H.sub.35 O.sub.8 N.sub.2 ]+ [C.sub.31 H.sub.33 O.sub.10     N.sub.2 ]+ [C.sub.31 H.sub.33 O.sub.10 N.sub.2 ]+ Proton NMR 2.82 (3H,s)     3.14 (3H,s) 4.64 2.85 (3H,s) 3.20 (3H,s) 4.97 1.80, 2.00, 2.05, 2.10     (each 1.81, 1.99, 2.02, 2.30 (each (DMSO-d.sub.6 , δ in ppm,     (2H,m) 6.04 (3H.m) 6.74 (1H,d, (2H,m) 5.16 (1H,m) 6.11 (1H,t) 3H,s) 2.87     (3H,s) 3.35 (3H,s) 3H,s) 2.85 (3H,s) 3.27 (3H,s) CD.sub.2 HSOCD.sub.3     proton J=8.5Hz,1'-H) 7.18 (1H,dd,J=2, 6.17 (1H,t) 7.01 (1H,d,J=5Hz, 4.26     (2H,m) 4.43 (1H,m) 5.57 4.24 (2H,m) 4.74 (1H,m) chemical shift (δ     9Hz) 8.53 (1H,d,J=7.5Hz) 8.35 1'-H) 7.18 (1H,dd,J=2,9Hz) (2H,m) 5.93     (1H,t) 6.38 (1H,d, 5.54 (3H,m) 6.42 (1H, 2.50 ) was used as (1H,d,J=7.5Hz     ) 9.51 (1H,s) 7.45-7.74 and 7.92-8.07 (15H, J=9Hz,1' -H) 7.20 (1H,dd,J=2,      d,J=8.5Hz,1'-H) 7.20 (1H,dd, internal standard, 10.23 (1H,s) 12.19     (1H,brs) m) 8.48 (1H,d,J=7.5Hz) 9Hz) 7.56 (1H,d,J=9Hz) 7.87 J=2,9Hz)     7.56 (1H,d,J=9Hz) Intensity of NMR (360MHz) 7.80 81H,d,J=2Hz) 8.70 (1H,     (1H,d,J=2Hz) 8.48 (1H,d, 7.87 (1H,d,J=2Hz) 8.51 (2H,s) magnetic field     was  d,J=7.5Hz) 9.46 (1H,s) 10.17 J=7.5Hz) 8.67 (1H,d,J=7.5Hz) 9.50     (1H,s) 10.06 (1H,s) indicated in each  (1H,s) 12.14 (1H,s) 9.48 (1H,s)     10.15 (1H,s) 12.23 (1H,brs) compound)  (360MHz) 12.20(1H,brs) (360MHz)      (360MHz) Elementary analysis C.sub.43 H.sub.35 N.sub.2 O.sub.8 Br     C.sub.43 H.sub.35 N.sub.2 O.sub.8 Br C.sub.31 H.sub.33 N.sub.2 O.sub.10     Br C.sub.31 H.sub.33 N.sub.2 O.sub.10 Br Molecular formula Calc. (C, H,     N) % 65.57, 4.48, 3.56 65.57, 4.48, 3.56 55.28, 4.79, 4.16 55.28, 4.79,     4.16 Found (C, H, N) % 65.60, 4.42, 3.31 65.37, 4.65, 3.41 55.15, 5.12,     4.26 55.25, 4.91, 4.32       Example No. 59 60 61 62       R      ##STR137##      ##STR138##      ##STR139##      ##STR140##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.-       Crystalline form Amorphous red powder Amorphous red powder Amorphous     red powder Amorphous red powder Specific rotatory +95° (C = 0.18,     MeOH) +17° (C = 0.15, MeOH) -21° (C =      0.21 MeOH) -290° (C = 0.16 1% CF.sub.3      COOH/ power [α].sub.D    H.sub.2 O) Infrared absorption 3400,     3100, 1725, 1640, 1600, 3427, 3189, 1754, 1639, 1598, 3427, 3189, 1754,     1639, 1598, 3370, 1647, 1606, 1483, 1425, (KBr, cm.sup.-1) 1590, 1475,     1450, 1430, 1250 1483, 1434, 1393, 1229 1483, 1434, 1393, 1229 1229,     1204, 1097 Ultraviolet Same as in compound 55 226 (ε15000) Same     as in the left 208 (ε19000) absorption  251 (ε19000)     227 (ε13000) (λ.sub.max.sup.EtOH, nm)  269 (ε25000     )  267 (ε22000)   327 (ε47000)  280 (ε19000)     324 (ε42000) Mass spectrum 707 535 535 425 (SIMS, m/z) [C.sub.43     H.sub.35 O.sub.8 N.sub.2 ].sup.+ [C.sub.29 H.sub.31 O.sub.8 N.sub.2     ].sup.+ [C.sub.29 H.sub.31 O.sub.8 N.sub.2 ].sup.+ [C.sub.23 H.sub.25     O.sub.6 N.sub.2      ].sup.+ Proton NMR Same as in compound 55 1.26 (3H,d,J=6.5Hz) Same as     in the left 2.85 (3H,s) 3.34 (3H,s) 4.85 (DMSO-d.sub.6, δ in ppm,     1.81, 2.00, 2.32 (each 3H,s)  (1H,t) 4.96, 5.25, 5.61 (each CD.sub.2     HSOCD.sub.3  proton  2.86 (3H,s) 3.35 (3H,s)  1H,d) 5.82 (1H,d,J=8.5Hz,1'     -H) chemical shift (δ  4.55 (1H,q) 5.38 (1H,d)  7.20 (1H,dd,J=2,9Hz     ) 7.56 (1H, 2.50) was used as  5.50 (2H,m) 6.38 (1H,d,  d,J=9Hz) 7.87     (1H,d,J=2Hz) internal standard,  J=8Hz,1'-H) 7.21 (1H,dd,  8.53 (2H,s)     9.48 (1H,s) 10.07 Intensity of NMR  J=2,9Hz) 7.57 (1H,d,J=9Hz)  (1H,s)     magnetic field was  7.87 (1H,d,J=2Hz) 8.50  (300MHz) indicated in each     (2H,s) 9.52 (1H,s) 10.08 compound)  (1H,s) 12.20 (1H,brs)   (300MHz)     Elementary analysis C.sub.43 H.sub.35 N.sub.2 O.sub.8 Br C.sub.29     H.sub.31 N.sub.2 O.sub.8 Br C.sub.29 H.sub.31 N.sub.2 O.sub.8 Br     C.sub.23 H.sub.25 N.sub.2 O.sub.6 Br Molecular formula Calc. (C, H, N) %     65.57, 4.48, 3.56 56.59, 5.08, 4.55 56.59, 5.08, 4.55 54.66, 5.00, 5.54     Found (C, H, N) % 65.32, 4.59, 3.60 56.71, 4.98, 4.32 56.72, 5.15, 4.32     54.41, 5.05, 5.73       Example No. 63 64 66 66      ##STR141##      ##STR142##      ##STR143##      ##STR144##      R (L-Ara) (D-Ara) (D-Man) (L-Man)       X.sup.- Br.sup.- Br.sup.- Br Br       Crystalline form Amorphous orange powder Amorphous red powder Amorphous      red powder Amorphous red powder Specific rotatory -38° (C =     0.11) +52° (C = 0.22) +300° C. (C = 0.27) -300° (C     = 0.24) power [α].sub.D Infrared absorption 3200, 1640, 1590,     1460, 1420, 3200, 1640, 1590, 1460, 1420, 3200, 1640, 1600, 1470, 1420,     3200, 1640, 1600, 1470, 1420, (KBr, cm.sup.-1) 1210, 1050, 800 1210,     1050, 800 1220, 1200, 1100, 1040, 800 1220, 1200, 1100, 1040, 800     Ultraviolet 227 (ε16000) 226 (ε15000) 209 (ε20000     ) 209 (ε20000) absorption 268 (ε25000) 268 (ε2400     0) 227 (ε14000) 226 (ε14000) (λ.sub.max.sup.EtOH,     nm) 280 (ε22000) 281 (ε22000) 267 (ε26000) 266     (ε25000)  323 (ε50000) 323 (ε47000) 280 (.epsilon     .21000) 280 (ε23000)    324 (ε49000) 324 (ε51000)      Mass spectrum (C.I.) 395 395 425 425 (SIMS, m/z) [C.sub.22 H.sub.23     N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+     [C.sub.23 H.sub.25 N.sub.2 O.sub.6 ].sup.+ [C.sub.23 H.sub.25 N.sub.2     O.sub.6 ].sup.+ Proton NMR Same as in compound 64 2.86 (3H,s) 3.70     (2H,m) 4.16 2.86 (3H,s) 3.70 (1H,m) 3.77 Same as in the left (DMSO-d.sub.     6, δ in ppm,  (1H,q) 4.36 (1H,q) 4.58 (1H,q) (1H,m) 3.95 (1H,m)     4.00 (1H,m) CD.sub.2 HSOCD.sub.3 proton  5.18 (1H,t) 5.68 (1H,d) 6.16     (1H,d) 4.10 (2H,m) 4.91 (1H,t) 5.44 chemical shift (δ  6.35     (1H,d,J=3Hz 1'-H) (1H,d) 5.48 (1H,d) 5.64 (1H,d) 2.50) was used as  7.18     (1H,dd,J=2,9Hz) 7.54 (1H, 6.15 (1H,d,J= 8.5Hz,1'-H) 7.18 internal     standard,  d,J=9Hz) 7.86 (1H,d,J=2Hz) (1H,dd,J=2,9Hz) 7.55 (1H,d,     Intensity of NMR  8.50 (1H,d,J=7.5Hz) 8.58 (1H, J=9Hz) 7.86 (1H,d,J=2Hz)     8.51 magnetic field was  d,J=7.5Hz) 9.44 (1H,s) 9.97 (1H,d,J=7.5Hz) 8.58     (1H,d, indicated in each  (1H,s) 12.03 (1H,brs) J=7.5Hz) 9.44 (1H,brs)     10.07 compound)   (1H,s) 12.06 (1H,brs) Elementary analysis C.sub.22     H.sub.23 N.sub.2 O.sub.5 Br.1.5H.sub.2 O C.sub.22 H.sub.23 N.sub.2     O.sub.5 Br.1.5H.sub.2 O -- -- Molecular formula Calc. (C, H, N) % 52.60,     5.22, 5.58 52.60, 5.22, 5.58 Found (C, H, N) % 52.51, 5.23, 5.61 52.49,     5.14, 5.41       Example No. 67 67 68 69      ##STR145##      ##STR146##      ##STR147##      ##STR148##      R (D-Tal) (L-Tal) (L-Gal) (D-All)       X.sup.- Br Br Br Br       Crystalline form Amorphous reddish orange powder Amorphous reddish     orange powder Amorphous reddish orange powder Amorphous yellow powder     Specific rotatory +410° (C = 0.13) -400° (C = 0.21)     +320° (C = 0.21) -380° (C = 0.28) power [α].sub.D     Infrared absorption 3250, 1640, 1600, 1480, 1420, 3250, 1640, 1600,     1480, 1420, 3200, 1640, 1590, 1470, 1420, 3300, 1640, 1600, 1470, 1420,     (KBr, cm.sup.-1) 1220, 1200, 1100, 1060, 820 1220, 1200, 1100, 1060, 820     1220, 1200, 1090, 810 1220, 1120, 1040, 820 Ultraviolet 204 (ε220     00) 204 (ε22000) 206 (ε22000) 207 (ε20000)     absorption 226 (ε15000) 226 (ε15000) 226 (ε15000)      226 (ε14000) (λ.sub.max.sup.EtOH, nm) 268 (ε25000     ) 268 (ε25000) 268 (ε26000) 268 (ε26000)  280     (ε23000) 280 (ε23000) 281 (ε23000) 280 (ε     23000)  324 (ε50000) 324 (ε50000) 324 (ε 50000)     324 (ε51000) Mass spectrum 425 425 425 425 (SIMS, m/z) [C.sub.23     H.sub.25 N.sub.2 O.sub.6 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.6     ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.6 ].sup.+ [C.sub.23 H.sub.25     N.sub.2 O.sub.6 ].sup.+ Proton NMR 2.83 (3H,s) 3.29 (3H,s) 3.74 Same as     in the left 2.83 (3H,s) 3.28 (3H,s) 3.70 2.83 (3H,s) 3.29 (3H,s) 4.74     (DMSO-d.sub.6, δ in ppm, (1H,m) 3.90 (1H,m) 4.03 (1H,m)  (3H,m)     3.90 (3H,m) 4.87 (1H, (1H,brs) 5.08 (1H,d) 5.40 CD.sub.2 HSOCD.sub.3     proton 4.09 (1H,m) 4.20 (2H,m) 4.73  brs) 4.97 (1H,d) 5.25 (1H,d)     (1H,brs) 5.52 (1H,d) chemical shift (δ (1H,brs) 5.29 (1H,d) 5.36     5.62 (1H,brs) 6.05 (1H,d,J=9Hz,1'-H) 2.50) was used as (1H,d) 5.57     (1H,d)  5.82 (1H,d,J=8.5Hz,1'-H) 7.18 7.18 (1H,dd,J=2,9Hz) internal     standard 6.09 (1H,d,J=9Hz,1'-H)  (1H,dd,J=2,9Hz) 7.53 (1H,d,J=9Hz) 7.83     Intensity of NMR 7.17 (1H,dd,J=2,9Hz)  7.54 (1H,d,J=9Hz) 7.84 (1H,d,J=2Hz     ) 8.44 (1H,d, magnetic field was 7.53 (1H,d,J=9Hz)  (1H,d,J=2Hz) 8.48     (2H,s) 9.46 J=7.5Hz) 8.58 (1H,d,J=7.5Hz) indicated in each 7.83 (1H,d,J=2     Hz) 8.43 (1H,d,  (1H,brs) 10.03 (1H,s) 12.05 9.44 (1H,brs) 10.05 (1H,s)     compound) J=7.5Hz) 8.57 (1H,d,J=7.5Hz)  (1H,brs) 12.06 (1H,brs)  9.43     (1H,brs) 10.05 (1H,s)  12.05 (1H,brs) Elementary analysis C.sub.23     H.sub.25 N.sub.2 O.sub.6 Br.1.5H.sub.2 O C.sub.23 H.sub.25 N.sub.2     O.sub.5 Br.1.5H.sub.2 O -- C.sub.23 H.sub.25 N.sub.2 O.sub.6 Br.H.sub.2     O Molecular formula Calc. (C, H, N) % 51.88, 5.30, 5.26 51.88, 5.30,     5.26  52.78, 5.20, 5.35 Found (C, H, N) % 51.61, 5.20, 5.26 51.79, 5.15,     5.23  52.76, 5.14, 5.31       Example No. 69 70 71 72      ##STR149##      ##STR150##      ##STR151##      ##STR152##      R (L-All) (L-Glc)  (D-2d Rib)       X.sup.- Br Br Br.sup.- Cl       Crystalline form Amorphous yellow powder Amorphous red powder Amorphous      red powder Amorphous red powder Specific rotatory +390° (C =     0.25) +310° (C = 0.17) -300° (C = 0.12, 1% CF.sub.3     COOH/H.sub.2 O) -88° (C = 0.20) power [α].sub.D Infrared     absorption 3300, 1640, 1600, 1470, 1420, 3250, 1640, 1600, 1470, 1420,     3200, 1640, 1590, 1470, 1420, 3230, 1600, 1470, 1430, 1220, (KBr,     cm.sup.-1) 1220, 1120, 1040, 820 1220, 1200, 1100, 1060, 810 1380, 1210,     1190, 1100, 1060, 810 Ultraviolet 207 (ε20000) 209 (ε2100     0) 207 (ε21000) 207 (ε18000) absorption 226 (ε140     00) 227 (ε14000) 226 (ε15000) 227 (ε13000)     (λ.sub.max.sup.EtOH, nm) 268 (ε26000) 267 (ε30000)      267 (ε24000) 249 (ε20000)  280 (ε23000) 281     (ε22000) 280 (ε21000) 267 (ε21000)  324 (.epsilon     .51000) 324 (ε50000) 323 (ε48000) 280 (ε19000)       321 (ε42000) Mass spectrum 425 425 409 (C.I.) 379 (SIMS, m/z)     [C.sub.23 H.sub.25 N.sub.2 O.sub.6 ].sup.+ [C.sub.23 H.sub.25 N.sub.2     O.sub.6 ].sup.+ [C.sub.23 H.sub.25 O.sub.5 N.sub.2 ].sup.+ [C.sub.22     H.sub.23 N.sub.2 O.sub.4 ].sup.+ Proton NMR same as in the left 2.85     (3H,s) 3.46-3.84 (6H,m) 1.53 (3H,d,J=7Hz) 2.85 (3H,s) 2.67 (1H,m) 2.84     (3H,s) 3.72 (DMSO-d.sub.6, δ in ppm,  4.79 (1H,t) 5.37 (1H,t) 3.30     (3H,s) 3.70, 4.00, 4.10, (3H,s) 3.77 (1H,m) 3.86 (1H,m) CD.sub.2     HSOCD.sub.3 proton  5.52 (1H,d) 5.71 (1H,d) 4.32 (each 1H,m) 5.38, 5.46,     4.16 (1H,m) 4.48 (1H,m) 5.55 (2H,m) chemical shift (δ  5.88     (1H,d,J=9Hz,1'-H) 5.63 (each 1H,d) 6.22 (1H,d, 6.67 (1H,t,J=6Hz,1'-H)     2.50) was used as  7.19 (1H,dd,J=2,9Hz) J=8.5Hz,1'-H) 7.17 (1H,dd, 7.16     (1H,dd,J=2,9Hz) 7.53 (1H, internal standard,  7.55 (1H,d,J=9Hz) 7.86     J=2,9Hz) 7.54 (1H,d,J=9Hz) d,J=9Hz) 7.83 (1H,d,J=2Hz) Intensity of NMR     (1H,d,J=2Hz) 8.47 (1H,d, 7.86 (1H,d,J=2Hz) 8.47 (1H,d, 8.47 (1H,d,J=7.5Hz     ) 8.68 (1H, magnetic field was  J=7.5Hz) 8.58 (1H,d,J=7.5Hz) J=7.5Hz)     8.56 (1H,d,J=7.5Hz) d,J=7.5Hz) 9.47 (1H,brs) 10.27 indicated in each     9.46 (1H,s) 10.05 (1H,s) 12.11 9.45 (1H,s) 10.08 (1H,s) (1H,s) 12.08     (1H,brs) compound)  (1H,brs) 12.08 (1H,brs) (360MHz) Elementary analysis     C.sub.23 H.sub.25 N.sub.2 O.sub.6 Br.H.sub.2 O -- C.sub.23 H.sub.25     N.sub.2 O.sub.5 Br.2H.sub.2 O -- Molecular formula Calc. (C, H, N) %     52.78, 5.20, 5.35  52.58, 5.56, 5.33 Found (C, H, N) % 52.59, 5.34, 5.29      52.61, 5.21, 5.35       Example No. 73 74 75 76      ##STR153##      ##STR154##      ##STR155##      ##STR156##      R (D-5d Rib) (L-5d Ara)       X.sup.- Cl Cl Br.sup.- Br.sup.-       Crystalline form Amorphous orange powder Amorphous red powder Amorphous      red powder Amorphous red powder Specific rotatory -240° (C =     0.17) -24° (C = 0.19) -210° (C = 0.14 1% CF.sub.3      COOH/H.sub.2 O) +190° (C = 0.19 1% CF.sub.3 COOH/H.sub.2 O)     power [α].sub.D Infrared absorption 3230, 1600, 1470, 1430, 1220,     3220, 1640, 1600, 1480, 1430, 3304, 1647, 1600, 1483, 1434, 3304, 1647,     1600, 1483, 1434, (KBr, cm.sup.-1) 1100, 1060, 820 1390, 1220, 1100,     1060, 920, 1220, 1155, 1106 1220, 1155, 1106   810 Ultraviolet 210     (ε19000) 209 (ε21000) 226 (ε15000) Same as in     the left absorption 226 (ε14000) 226 (ε15000) 267     (ε25000) (λ.sub.max.sup.EtOH, nm) 268 (ε23000)     267 (ε25000) 280 (ε22000)  325 (ε46000) 279     (ε22000) 324 (ε49000)   323 (ε50000) Mass     spectrum (C.I.) 379 (C.I.) 379 409 409 (SIMS, m/z) [C.sub.22 H.sub.23     N.sub.2 O.sub.4 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.4 ].sup.+     [C.sub.23 H.sub.25 O.sub.5 N.sub.2 ].sup.+ [C.sub.23 H.sub.25 O.sub.5     N.sub.2      ].sup.+ Proton NMR 1.53 (3H,d,J=6.5Hz) 2.86 (3H, 1.44 (3H,d,J=6.5Hz)     2.86 (3H, 1.30 (3H,d,J=6.5Hz) 2.85 (3H, same as in the left (DMSO-d.sub.6     , δ in ppm, s) 3.96 (1H,q) 4.32 (1H,m) 4.39 s) 3.91 (1H,m) 4.35     (1H,m) 4.71 s) 3.65 (2H,m) 3.87 (1H,m) CD.sub.2 HSOCD.sub.3 proton     (1H,t) 5.54 (1H,d) 5.88 (1H,d) (1H,m) 5.71 (1H,d) 6.24 (1H,d) 4.04     (1H,q) 4.96, 5.20, 5.56 chemical shift (δ 6.28 (1H,d,J=5.5Hz,1'-H) 6     .39 (1H,d,J=2.5Hz,1'-H) (each 1H,d) 5.78 (1H,d,J=9Hz, 2.50) was used as     7.18 (1H,dd,J=2,9Hz) 7.18 (1H,dd,J=2,9Hz) 1'-H) 7.19 (1H,dd,J=2,9Hz)     internal standard, 7.54 (1H,d,J=9Hz) 7.84 (1H,d, 7.55 (1H,d,J=9Hz) 7.86     (1H,d, 7.56 (1H,d,J= 9Hz) 7.86 (1H,d, Intensity of NMR J=2Hz) 8.43     (1H,d,J=7.5Hz) J=2Hz) 8.48 (1H,d,J=7.5Hz) 8.57 J=2Hz) 8.52 (2H,q) 9.46     (1H,s) magnetic field was 8.48 (1H,d,J=7.5Hz) 9.49 (1H,d,J=7.5Hz) 9.46     (1H,brs) 10.04 (1H,s) 12.10 (1H,brs) indicated in each (1H,brs) 9.98     (1H,s) 12.08 9.96 (1H,s) 12.07 (1H,brs) (300MHz) compound) (1H,brs)     Elementary analysis -- C.sub.22 H.sub.23 N.sub.2 O.sub.4 Cl.2H.sub.2 O     C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br C.sub.23 H.sub.25 N.sub.2 O.sub.5     Br Molecular formula Calc. (C, H, N) %  58.59, 6.04, 6.21 56.45, 5.15,     5.73 56.45, 5.15, 5.73 Found (C, H, N) %  58.91, 5.64, 6.61 56.63, 5.01,     5.95 56.71, 5.01, 5.69       Example No. 77 77 78 79      ##STR157##      ##STR158##      ##STR159##      ##STR160##      R (D-Xyl) (L-Xyl) (D-Xyl) (D-Ery)       X.sup.- Cl Cl Br Cl       Crystalline form Amorphous yellow powder Amorphous yellow powder     Amorphous yellowish orange Amorphous reddish orange    powder powder     Specific rotatory +150° (C = 0.17) -170° (C = 0.35)     +140° (C = 0.22) -240° (C = 0.14) power [α].sub.D     Infrared absorption 3260, 1640, 1590, 1500, 1470, 3260, 1640, 1590,     1500, 1470, 3270, 1650, 1600, 1480, 1430, 3220, 1600, 1470, 1430, 1220,     (KBr, cm.sup.-1) 1420, 1320, 1210, 1090, 1020, 1420, 1320, 1210, 1090,     1020, 1390, 1220, 1100, 840, 810, 1110, 1060, 820  830, 800, 720 830,     800, 720 720 Ultraviolet 210 (ε21000) 209 (ε22000) 226     (ε17000) 210 (ε18000) absorption 226 (ε15000)     226 (ε16000) 268 (ε26000) 226 (ε13000) (λ.     sub.max.sup.EtOH, nm) 268 (ε26000) 267 (ε26000) 280     (ε23000) 267 (ε22000)  280 (ε23000) 280 (.epsilon     .24000) 322 (ε52000) 324 (ε45000)  322 (ε51000)     322 (ε52000) Mass spectrum 395 395 395 365 (SIMS, m/z) [C.sub.22     H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5     ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.21 H.sub.21     N.sub.2 O.sub.4 ].sup.+ Proton NMR 2.78 (3H,s) 3.22 (2H,s) 3.97 same as     in the left 2.83 (3H,s) 3.26 (3H,s) 3.96 2.85 (3H,s) 3.30 (3H,s) 4.09     (DMSO-d.sub.6, δ in ppm, (2H,m) 4.15 (1H,d) 4.34 (1H,s)  (2H,m)     4.15 (1H,d) 4.34 (1H,s) (1H,d) 4.28 (1H,m) 4.44 (1H,t) CD.sub.2      HSOCD.sub.3 proton 4.49 (1H,q) 5.12 (1H,brs) 5.73  4.49 (1H,q) 5.14     (1H,brs) 5.79 4.72 (1H,dd) 5.58 (1H,d) 5.94 (1H,d) chemical shift     (δ (1H,brs) 6.39 (1H,brs)  (1H,brs) 6.39 (1H,brs) 6.26, (1H,d,J=6.5     Hz,1'-H) 2.50) was used as 6.32 (1H,s,1'-H)  6.30 (1H,s,1'-H) 7.18     (1H,dd,J=2,9Hz) internal standard, 7.16 (1H,dd,J=2,9Hz)  7.17 (1H,dd,J=2,     9Hz) 7.53 (1H,d,J=9Hz) 7.84 (1H,d, Intensity of NMR 7.50 (1H,d,J=9Hz)     7.78  7.53 (1H,d,J=9Hz) 7.83 J=2Hz) 8.47 (1H,d,J=7.5Hz) magnetic field     was (1H,d,J=2Hz) 8.44 (1H,d,  (1H,d,J=2Hz) 8.48 (1H,d, 8.54 (1H,d,J=7.5Hz     ) 9.48 (1H, indicated in each J=7.5Hz) 8.62 (1H,d,J=7.5Hz)  J=7.5Hz)     8.61 (1H,d,J=7.5Hz) s) 10.01 (1H,s) 12.15 (1H, compound) 9.47 (1H,brs)     10.00 (1H,s)  9.52 (1H,brs) 10.10 (1H,s) brs)  12.05 (1H,brs)  12.07     (1H,brs) Elementary analysis C.sub.22 H.sub.23 N.sub.2 O.sub.5      Cl.H.sub.2 O C.sub.22 H.sub.23 N.sub.2 O.sub.5 Cl.H.sub.2 O -- C.sub.21     H.sub.21 N.sub.2 O.sub.4 Cl.2H.sub.2 O Molecular formula Calc. (C, H, N)     % 58.86, 5.61, 6.24 58.86, 5.61, 6.24  57.72, 5.77, 6.41 Found (C, H, N)     % 58.77, 5.32, 6.35 58.67, 5.37, 6.27  57.41, 5.49, 6.42       Example No. 79 80 81 82      ##STR161##      ##STR162##      ##STR163##      ##STR164##      R (L-Eryl) (L-Rib) (D-Rib) (L-Rib)       X.sup.- Cl Br Br Br       Crystalline form Amorphous reddish orange Amorphous red powder     Amorphous red powder Amorphous orange powder Specific rotatory +220.degre     e. (C = 0.23) +310° (C = 0.28) -330° (C =      0.20) +190° (C = 0.11) power [α].sub.D Infrared absorption     3220, 1600, 1470, 1430, 1220, 3200, 1640, 1600, 1430, 1260, 3250, 1640,     1600, 1480, 1430, 3200, 1640, 1580, 1460, 1220, (KBr, cm.sup.-1) 1110,     1060, 820 1190, 1100, 1050, 800 1220, 1180, 1100, 1040, 980, 1100, 800      820, Ultraviolet 210 (ε18000) 222 (ε15000) 209 (.epsilon     .21000) 206 (ε20000) absorption 226 (ε13000) 268     (ε25000) 226 (ε15000) 226 (ε15000) (λ.sub.     max.sup.EtOH, nm) 267 (ε22000) 281 (ε22000) 268 (.epsilon     .26000) 267 (ε25000)  324 (ε45000) 324 (ε50000)     281 (ε23000) 280 (ε22000)    324 (ε51000) 324     (ε48000) Mass spectrum 365 395 (C.I.) 395 395 (SIMS, m/z)     [C.sub.21 H.sub.21 N.sub.2 O.sub.4 ].sup.+ [C.sub.22 H.sub.23 N.sub.2     O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22     H.sub.23 N.sub.2 O.sub.5 ].sup.+ Proton NMR Same as in the left Same as     in compound 81 2.86 (3H,s) 3.87 (2H,m) 3.94 2.81 (3H,s) 3.33 (3H,s)     3.81, (DMSO-d.sub.6, δ in ppm,   (2H,m) 4.08 (1H,m) 5.11 (1H,d)     3.93 (each 1H,m) 4.26 (2H,m) CD.sub.2 HSOCD.sub.3 proton   5.38 (1H,d)     5.47 (1H,d) 4.35 (1H,m) 5.47 (1H,d) chemical shift (δ   5.98     (1H,d,J=9Hz,1'-H) 5.89 (1H,d) 5.64 (1H,t) 2.50) was used as   7.18     (1H,dd,J=2,9Hz) 6.28 (1H,d,J=5Hz,1'-H) internal standard,   7.56     (1H,d,J=9Hz) 7.16 (1H,dd,J=2, Intensity of NMR   7.87 (1H,d,J=2Hz) 8.46     (1H,d, 9Hz) 7.50 (1H,d,J=9Hz) 7.79 magnetic field was   J=7.5Hz) 8.56     (1H,d,J=7.5Hz) (1H,d,J=2Hz) 8.46 (1H,d, indicated in each   9.44 (1H,s)     10.06 (1H,s) 12.09 J=7.5Hz) 8.64 (1H,d,J=7.5Hz) compound)   (1H,brs)     9.44 (1H,s) 10.23 (1H,s) 12.04     (1H,s) Elementary analysis C.sub.21     H.sub.21 N.sub.2 O.sub.4 Cl.2H.sub.2 O C.sub. 22 H.sub.23 N.sub.2     O.sub.5 Br.1.5H.sub.2 O C.sub.22 H.sub.23 N.sub.2 O.sub.5 Br.1.5H.sub.2     O Molecular formula Calc. (C, H, N)% 57.72, 5.77, 6.41 52.60, 5.22, 5.58     52.60, 5.22, 5.58 Found (C, H, N)% 57.80, 5.53, 6.40 52.80, 5.08, 5.66     52.97, 5.07, 5.62       Example No. 83 84 85 86      ##STR165##      ##STR166##      ##STR167##      ##STR168##      R  (D-Ara) (L-Ara) (D-Lyx)       X.sup.- Br.sup.- Br Br Cl       Crystalline form Amorphous orange powder Amorphous red powder Amorphous      orange powder Amorphous reddish orange     powder Specific rotatory     -180° (C = 0.16, 1(v/v %) +230° (C = 0.20) -240° (C     = 0.19) +250° (C = 0.42) power [α].sub.D CF.sub.3 CO.sub.2     H/H.sub.2 O) Infrared absorption 3222, 1647, 1598, 1483, 1434, 3250,     1640, 1590, 1420, 1190, 3250, 1640, 1600, 1480, 1420, 3240, 1600, 1470,     1430, 1220, (KBr, cm.sup.-1) 1393, 1294, 1220, 1106 1140, 1090, 920,     810, 740 1220, 1200, 1150, 1090, 1060, 1150, 1100, 820    810 Ultraviolet      226 (ε13000) 227 (ε14000) 227 (ε14000) 209     (ε17000) absorption 268 (ε23000) 267 (ε25000)     268 (ε24000) 227 (ε13000) (λ.sub.max.sup.EtOH,     nm) 281 (ε20000) 281 (ε22000) 281 (ε21000) 267     (ε20000)  323 (ε46000) 324 (ε48000) 325 (.epsilon     .47000) 323 (ε42000) Mass spectrum 395 (C.I.) 395 395 395 (SIMS,     m/z) [C.sub.22 H.sub.23 O.sub.5 N.sub.2 ].sup.+ [C.sub.22 H.sub.23     N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+     [C.sub. 22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ Proton NMR 2.84 (3H,s) 3.35     (3H,s) 3.80, 2.85(3H,s) 3.65 (1H,m) 3.90 Same as in compound 84 2.84     (3H,s) 3.26 (3H,s) 3.68 (DMSO-d.sub.6, δ in ppm, 3.92 (each 1H,q)     4.26 (2H,m) (3H,m) 4.08 (1H,d) 5.12 (1H,d)  (1H,m) 3.80 (1H,m) 4.23     (1H,m) CD.sub.2 HSOCD.sub.3 proton 4.34 (1H,m) 5.47, 5.85, (each 5.24     (1H,d) 5.61 (1H,d)  4.55 (1H,brs) 4.79 (1H,m) 4.91 chemical shift     (δ 1H,d,) 5.62 (1H,t) 6.28 (1H,d, 5.74 (1H,d,J=8.5Hz,1'-H)  4.91     (1H,t) 5.57 (1H,d) 5.94 (1M,brs) 2.50) was used as J=5Hz,1'-H) 7.18     (1H,dd,J=2, 7.18 (1H,dd,J=2,9Hz)  6.27 (1H,d,J=6.5Hz,1'-H) internal     standard, 9Hz) 7.54 (1H,d,J=9Hz) 7.85 7.55 (1H,d,J=9Hz)  7.16 (1H,dd,J=2,     9Hz) Intensity of NMR (1H,d,J=2Hz) 8.52 (1H,d, 7.86 (1h,d,J=2Hz) 8.51     (2H,  7.53 (1H,d,J=9Hz) 7.82 (1H, magnetic field was J=7.5Hz) 8.63     (1H,d,J=7.5Hz) AB quartet) 9.45 (1H,brs)  brs) 8.46 (1H,d,J=9Hz) 8.54     indicated in each 9.45 (1H,s) 10.26 (1H,s) 12.04 10.03 (1H,s) 12.08     (1H,brs)  (1H,d,J=7.5Hz) 9.48 (1H,brs) compound) (1H,brs)   9.99 (1H,s)     12.14 (1H,brs)  (360MHz) Elementary analysis C.sub.22 H.sub.23 N.sub.2     O.sub.5 Br C.sub.22 H.sub.23 N.sub.2 O.sub.5 Br.2H.sub.2 O C.sub.22     H.sub.23 N.sub.2 O.sub.5 Br.2H.sub.2 O -- Molecular formula Calc. (C, H,     N)% 55.59, 4.88, 5.89 51.67, 5.32, 5.48 51.67, 5.32, 5.48 Found (C, H,     N)% 55.41, 4.90, 5.99 51.71, 5.06. 5.37 51.57, 5.31, 5.40       Example No. 87 88 89 90      ##STR169##      ##STR170##      ##STR171##      ##STR172##      R (L-Lyx) (L-Lyx) (D-Lyx) (D-Glc NAc)       X.sup.- Cl Cl Cl Cl       Crystalline form Amorphous reddish orange Amorphous orange powder     Amorphous orange powder Amorphous reddish orange  powder   powder     Specific rotatory -280° (C = 0.14) -320° (C = 0.19)     +400° (C = 0.09) -280° (C = 0.10) power [α].sub.D     Infrared absorption 3240, 1600, 1470, 1430, 1220, 3250, 1640, 1600,     1480, 1420, 3250, 1640, 1600, 1480, 1420, 3250, 1660, 1590, 1480, 1420,     (KBr, cm.sup.-1) 1150, 1100, 820 1220, 1180, 1050, 810 1220, 1180, 1050,     810 1290, 1220, 1050, 800 Untraviolet 208 (ε20000) 210 (ε     20000) 209 (ε20000) 227 (ε15000) absorption 226 (.epsilon     .15000) 226 (ε14000) 226 (ε14000) 269 (ε25000)     (λ.sub.max.sup.EtOH, nm) 267 (ε24000) 268 (ε24000)      268 (ε25000) 326 (ε47000)  324 (ε48000) 281     (ε22000) 280 (ε22000)   324 (ε49000) 324     (ε49000) Mass spectrum 395 395 395 466 (SIMS m/z) [C.sub.22     H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5     ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.25 H.sub.28     N.sub.3 O.sub.6 ].sup.+ Proton NMR same as in compound 86 same as in     compound 89 2.86 (3H,s) 3.74 (1H,m) 4.00 1.52 (3H,s) 2.84 (3H,s) 3.30     (DMSO-d.sub.6, δ in ppm,   (3H,m) 4.16 (1H,d) 5.38 (1H,d) (3H,s)     3.63 (4H,m) 3.85 (1H,m) CD.sub.2 HSOCD.sub.3 proton   5.48 (1H,d) 5.69     (1H,d) 4.10 (1H,q,J=9.5Hz) 4.48 chemical shift (δ   6.02 (1H,d,J=9H     z,1'-H) (1H,t) 5.48 (2H,m) 2.50) was used as   7.18 (1H,dd,J=2,9Hz) 5.93     (1H,d,J=9.5Hz,1'-H) internal standard,   7.55 (1H,d,J=9Hz) 7.18 (1H,dd,J=     2,9Hz) Intensity of NMR   7.87 (1H,d,J=2Hz) 8.50 (1H,d, 7.54 (1H,d,J=2Hz)      magnetic field was   J=7.5Hz) 8.55 (1H,d,J=7.5Hz) 7.85 (1H,d,J=2Hz)     8.26 (1H,d, indicated in each 9.46 (1H,brs) 10.07 (1H,s) J=9.5Hz) 8.41     (1H,d,J=7.5Hz) compound)   12.13 (1H,brs) 8.54 (1H,d,J=7.5Hz) 9.49 (1H,        s) 9.98 (1H,s) 12.14 (1H,s) Elementary analysis -- C.sub.22 H.sub.23     N.sub.2 O.sub.5 Cl.1.5H.sub.2 O C.sub.22 H.sub.23 N.sub.2 O.sub.5     Cl.1.5H.sub.2 O -- Molecular formula Calc. (C, H, N)%  57.70, 5.72, 6.12     57.70, 5.72, 6.12 Found (C, H, N)%  57.32, 5.33, 5.96 57.56, 5.49,     6.05    Example No. 91 92 93 94      ##STR173##      ##STR174##      ##STR175##      ##STR176##      R (D-Gal NAc) (D-Glc UAm) (D-Xyl) (L-Xyl)       X.sup.- Cl Br Br Br       Crystalline form Amorphous reddish orange Amorphous orange powder     Amorphous orange powder Amorphous orange powder  powder Specific     rotatory -190° (C = 0.13) -220° (C = 0.13) -230° (C     = 0.12) +260° (C =      0.16) power [α].sub.D Infrared absorption 3230, 1660, 1590, 1470,     1420, 3300, 1680, 1640, 1600, 1470, 3250, 1640, 1600, 1480, 1430, 3250,     1640, 1600, 1480, 1430, (KBr, cm.sup.-1) 1290, 1220, 1100, 800 1420,     1200, 1090, 800 1200, 1100, 1060, 810 1200, 1100, 1060, 810 Ultraviolet     206 (ε19000) 226 (ε15000) 206 (ε22000) 226     (ε13000) absorption 227 (ε13000) 268 (ε25000)     226 (ε15000) 268 (ε24000) (λ.sub.max.sup.EtOH,     nm) 269 (ε22000) 325 (ε48000) 268 (ε26000) 281     (ε21000)  326 (ε43000)  325 (ε50000) 324     (ε47000) Mass spectrum 466 438 395 (C.I.) 395 (SIMS, m/z)     [C.sub.25 H.sub.28 N.sub.3 O.sub.6 ].sup.+ [C.sub.23 H.sub.24 N.sub.3     O.sub.6 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22     H.sub.23 N.sub.2 O.sub.5 ].sup.+ Proton NMR 1.53 (3H,s) 2.84 (3H,s)     3.67- 2.86 (3H,s) 3.50 (1H,m) 3.75 2.86 (3H,s) 3.72 (3H,m) 4.10 Same as     in compound 93 (DMSO-d.sub.6, δ in ppm, 3.91 (5H,m) 4.41 (1H,q)     4.88 (2H,m) 3.95 (1H,d) 5.52 (1H,d) (1H,q) 5.36 (1H,d) 5.55 CD.sub.2     HSOCD.sub.3 proton (1H,t) 5.14 (1H,d) 5.18 (1H,d) 5.65 (1H,d) 5.78     (1H,d) (1H,d) 5.72 (1H,d) chemical shift (δ 5.82 (1H,d,J=9.5Hz,1'-H     ) 7.19 5.93 (1H,d,J=9Hz,1'-H) 5.80 (1H,d,J= 9Hz,1'-H) 2.50) was used as     (1H,dd,J=2,9Hz) 7.56 (1H,d, 7.18 (1H,dd,J=2,9Hz) 7.18 (1H,dd,J=2,9Hz)     internal standard, J=9Hz) 7.87 (1H,d,J=2Hz) 8.14 7.41 (1H,s) 7.73,(1H,     7.56 (1H,d,J=9Hz) Intensity of NMR (1H,d,J=9Hz) 8.48 (2H,ABq s) 7.56     (1H,d,J=9Hz) 7.86 (1H, 7.86 (1H,d,J=2Hz) 8.46 (1H,d, magnetic field was     type) 9.48 (1H,brs) 9.97 d,J=2Hz) 8.48 (1H,d,J=7.5Hz) J=7.5Hz) 8.56     (1H,d,J=7.5Hz) indicated in each (1H,s) 12.13 (1H,brs) 8.55 (1H,d,J=7.5Hz     ) 9.48 (1H, 9.45 (1H,brs) 10.03 (1H,s) compound)  brs) 10.06 (1H,s)     12.13 (1H,brs) 12.08 (1H,brs) Elementary analysis C.sub.25 H.sub.28     N.sub.3 O.sub.6 Cl.3.5H.sub.2 O C.sub.23 H.sub.24 N.sub.3 O.sub.6     Br.H.sub.2 O C.sub.22 H.sub.23 N.sub.2 O.sub.5 Br.2H.sub.2 O C.sub.22     H.sub.23 N.sub.2 O.sub.5 Br.2H.sub.2 O Molecular formula Calc. (C, H,     N)% 53.14, 6.24, 7.44 51.50, 4.89, 7.83 51.67, 5.32, 5.48 51.67, 5.32,     5.48 Found (C, H, N)% 53.52, 5.96, 7.36 51.21, 4.98, 7.51 51.53, 5.12,     5.29 51.32, 4.92, 5.21       Example No. 95 96 96 97      ##STR177##      ##STR178##      ##STR179##      ##STR180##      R  (D-Ara) (L-Ara) (L-5d Ara)       X.sup.- CH.sub.3      CO.sub.2.sup.- AcO AcO AcO                              Crystalline     form Amorphous orange powder Amorphous dark red powder Amorphous dark     red powder Amorphous dark red powder Specific rotatory -360° (C =     0.28, H.sub.2 O) -800 (λ = 320 nm) +690 (λ = 320 nm) +590     (λ = 314 nm) power [α].sub.D -280° (C = 0.36 1%     CF.sub.3 COOH/ -610 (λ = 262 nm) +560 (λ = 256 nm) -720     (λ = 227 nm)  H.sub.2 O) +340 (λ = 231 nm) -470 (λ     = 229 nm) Infrared absorption 3238, 1638, 1598, 1565, 1475, 3200, 1600,     1480, 1400, 1290, 3180, 1600, 1480, 1400, 1290, 3170, 1590, 1470, 1400,     1220 (KBr, cm.sup.-1) 1409, 1220, 1056 1220, 1120, 1070, 810 1220, 1120,     1070, 810 1060, 920, 800 Ultraviolet 226 (ε13000) 210 (ε1     9000) 210 (ε18000) 208 (ε18000) absorption 267 (ε     23000) 226 (ε15000) 227 (ε14000) 226 (ε15000)     (λ.sub.max.sup.EtOH, nm) 281 (ε20000) 266 (ε23000)      266 (ε23000) 266 (ε21000)  333 (ε47000) 281     (ε21000) 280 (ε21000) 280 (ε20000)   322     (ε45000) 322 (ε46000) 322 (ε37000) Mass spectrum     409 395 395 (C.I.) 379 (SIMS, m/z) [C.sub.23 H.sub.25 O.sub.5 N.sub.2     ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23     N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.4 ].sup.+     Proton NMR 1.53 (3H,d,J=7Hz) 1.68 (3H,s) Broad signal observed in Same     as in the left DMSO-d.sub.6 (CF.sub.3 CO.sub.2 H 1 drop (DMSO-d.sub.6,     δ in ppm 2.78 (3H,s) 3.23 (3H,s) DMSO-d.sub.6  addition CD.sub.2     HSOCD.sub.3 proton 3.68, 4.03, 4.07, 4.29 (each   1.58 (3H,d,J=6.5Hz)     chemical shift (δ 1H,m) 6.24 (1H,d,J=8.5Hz,   1.90 (3H,s) 2.85     (3H,s) 2.50) was used as 1'-H) 7.14 (1H,dd,J=2,9Hz)   3.30 (3H,s) 3.88     (1H,t) internal standard, 7.51 (1H,d,J=9Hz) 7.80 (1H,   4.18 (1H,m) 4.41     (1H,t) Intensity of NMR d,J=2Hz) 8.36 (1H,d,J=7.5Hz)   6.59 (1H,d,J=5Hz,1     '-H) magnetic field was 8.51 (1H,d,J=7.5Hz) 10.03   7.17 (1H,dd,J=2,9Hz)     indicated in each (1H,s) (300MHz)   7.53 (1H,d,J=9Hz) 7.84 compound)     (1H,d,J=2Hz) 8.38 (1H,d,     J=7.5Hz) 8.44 (1H,d,     J=7.5Hz) 9.90     (1H,s)     12.01 (1H,s) Elementary analysis C.sub.25 H.sub.28 N.sub.2     O.sub.7 -- -- -- Molecular formula Calc. (C, H, N)% 64.09, 6.02, 5.98     Found (C, H, N)% 64.09, 5.93, 5.95       Example No. 98 98 99 99      ##STR181##      ##STR182##      ##STR183##      ##STR184##      R (D-Rib) (L-Rib) (D-Lyx) (L-Lyx)       X.sup.- AcO AcO AcO AcO       Crystalline form Amorphous reddish orange powder Amorphous reddish     orange powder Amorphous reddish orange powder Amorphous reddish orange     powder Specific rotatory -300° (C = (0.18) +300° (C =     0.20) +300° (C = 0.23) -310° (C =      0.17) power [α].sub.D Infrared absorption 3200, 1640, 1590, 1410,     1180, 3200, 1640, 1590, 1410, 1180, 3200, 1640, 1590, 1400, 1210, 3200,     1640, 1590, 1400, 1210, (KBr, cm.sup.-1) 1100, 1040, 820 1100, 1040, 820     1140, 1100, 1050, 820 1140, 1100, 1050, 820 Ultraviolet 205 (ε270     00) 205 (ε27000) 210 (ε21000) 210 (ε21000)     absorption 225 (ε19000) 225 (ε 19000) 226 (ε15000     ) 226 (ε15000) (λ.sub.max.sup.EtOH, nm) 269 (ε2800     0) 269 (ε28000) 268 (ε25000) 268 (ε25000)  324     (ε51000) 324 (ε51000) 324 (ε50000) 324 (ε     50000)Mass spectrum 395 395 395 395 (SIMS, m/z) [C.sub.22 H.sub.23     N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+     [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2     O.sub.5 ].sup.+ Proton NMR 1.71 (3H,s) 2.71 (3H,s) Same as in the left     1.70 (3H,s) 2.72 (3H,s) Same as in the left (DMSO-d.sub.6, δ in     ppm, 3.13 (3H,s) 3.88 (4H,m)  3.11 (3H,s) 3.67 (1H,q) CD.sub.2      HSOCD.sub.3 proton 4.15 (1H,s) 5.97 (1H,d,  3.81 (1H,q) 4.24 (1H,t)     chemical shift (δ J=9Hz,1'-H) 7.12 (1H,dd,  4.49 (1H,q) 4.75     (1H,m) 2.50) was used as J=2,9Hz) 7.47 (1H,d,  6.23 (1H,d,J=7Hz,1'-H)     internal standard, J=9Hz) 7.74 (1H,d,J=2Hz)  7.10 (1H,dd,J=2,9Hz)Intensit     y of NMR 8.24 (1H,d,J=7.5Hz)  7.45 (1H,d,J=9Hz) magnetic field was 8.43     (1H,d,J=7.5Hz)  7.72 (1H,d,J=2Hz) indicated in each 9.90 (1H,s)  8.19     (1H,d,J=7.5Hz) compound)   8.33 (1H,d,J=7.5Hz)    9.82 (1H,s) Elementary     analysis Molecular formula Calc. (C, H, N) % Found (C, H, N) %       Example No. 100 100 101 101      ##STR185##      ##STR186##      ##STR187##      ##STR188##      R (L-Fuc) (D-Fuc) (D-Ara) (L-Ara)       X.sup.- AcO AcO AcO AcO       Crystalline form Amorphous reddish orange powder Amorphous reddish     orange powder Amorphous brown-dark brown Amorphous brown-dark    powder     powder Specific rotatory +210° (C = (0.18) -200° (C =     0.23) +300° (C =  0.16) -290° (C =      0.15) power [α].sub.D Infrared absorption 3200, 1640, 1590, 1480,     1410, 3200, 1640, 1590, 1480, 1410, 3200, 1650, 1600, 1460, 1420, 3200,     1650, 1600, 1460, 1420, (KBr, cm.sup.-1) 1200, 1150, 1100, 810 1200,     1150, 1100, 810 1100, 930, 820 1100, 930, 820 Ultraviolet 210 (ε2     0000) 210 (ε20000) 207 (ε22000) 207 (ε22000)     absorption 226 (ε14000) 226 (ε14000) 225 (ε15000)      225 (ε15000) (λ.sub.max.sup.EtOH, nm) 267 (ε23000     ) 267 (ε23000) 268 (ε25000) 268 (ε25000)  281     (ε20000) 281 (ε20000) 325 (ε47000) 325 (ε     47000)  325 (ε44000) 325 (ε44000) Mass spectrum 409 409     395 395 (SIMS, m/z) [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub.23     H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5     ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ Proton NMR 1.30     (3H,d,J=6.5Hz) Same as in the left 1.68 (3H,s) 2.64 (3H,s) Same as in     the left (DMSO-d.sub. 6, δ in ppm, 1.68 (3H,s) 2.68 (3H,s)  3.01     (3H,s) 3.67 (1H,m) CD.sub.2 HSOCD.sub.3 proton 3.07 (3H,s) 3.67 (2H,m)     3.87 (2H,m) 3.97 (1H,t) chemical shift (δ 3.93 (1H,t) 4.02 (1H,q)     4.04 (1H,m) 2.50) was used as 5.76 (1H,d,J=9Hz,1'-H)  5.60 (1H,d,J=8.5Hz,     1'-H) internal standard, 7.13 (1H,d,J=2,9Hz)  7.09 (1H,dd,J=2,9Hz)     Intensity of NMR 7.49 (1H,d,J=9Hz)  7.48 (1H,d,J=9Hz) magnetic field was     7.74 (1H,s) 8.27 (1H,d,  7.70 (1H,d,J=2Hz) 8.12 indicated in each     J=7.5Hz) 8.38 (1H,d,J=7.5Hz)  (1H,d,J=7.5Hz) 8.22 (1H,d, compound) 9.85     (1H,s)  J=7.5Hz) 9.60 (1H,s) Elementary analysis Molecular formula Calc.     (C, H, N) % Found (C, H, N) %      Example No. 102 102 103 103      ##STR189##      ##STR190##      ##STR191##      ##STR192##      R (L-Gal) (D-Gal) (D-Lyx) (L-Lyx)       X.sup.- AcO AcO AcO AcO       Crystalline form Amorphous brown-dark brown Amorphous brown-dark brown     Amorphous reddish orange powder Amorphous reddish orange powder  powder     powder Specific rotatory +300° (C = (0.19) -310° (C =     0.22) +410° (C = 0.17) -350° (C =      0.23) power [α].sub.D Infrared absorption 3250, 1640, 1580, 1410,     1200, 3250, 1640, 1580, 1410, 1200, 3200, 1640, 1590, 1420, 1300, 3200,     1640, 1590, 1420, 1300, (KBr, cm.sup.-1) 1090, 880, 800 1090, 880, 800     1220, 1180, 1080, 820 1220, 1180, 1080, 820 Ultraviolet 206 (ε230     00) 206 (ε23000) 208 (ε22000) 208 (ε22000)     absorption 226 (ε16000) 226 (ε16000) 226 (ε15000)      226 (ε15000) (λ.sub.max.sup.EtOH, nm) 269 (ε26000     ) 269 (ε26000) 267 (ε25000) 267 (ε25000)  280     (ε23000) 280 (ε23000) 281 (ε22000) 281 (ε     22000)  324 (ε 49000) 324 (ε49000) 324 (ε50000)     324 (ε50000) Mass spectrum 425 425 395 395 (SIMS, m/z) [C.sub.23     H.sub.25 N.sub.2 O.sub.6 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.6     ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23     N.sub.2 O.sub.5 ].sup.+ Proton NMR Same as in the right 1.70 (3H,s) 2.58     (3H,s) 1.71 (3H,s) 2.71 (3H,s) Same as in the left (DMSO-d.sub.6,     δ in ppm,  2.98 (3H,s) 3.68 (3H,m) 3.13 (3H,s) 3.73 (1H,d)     CD.sub.2 HSOCD.sub.3 proton  3.87 (2H,m) 3.96 (1H,t) 3.93 (1H,d) 4.05     (2H,m) chemical shift (δ  5.74 (1H,d,J=9Hz,1'-H) 4.17 (1H,d) 2.50)     was used as  7.12 (1H,dd,J=2,9Hz) 6.02 (1H,d,J=9Hz,1'-H) internal     standard,  7.45 (1H,d,J=9Hz) 7.11 (1H,dd,J=2,9Hz) Intensity of NMR  7.68     (1H,d,J=2Hz) 7.47 (1H,d,J=9Hz) magnetic field was  8.17 (1H,d,J=7.5Hz)     8.33 7.73 (1H,d,J=2Hz) indicated in each  (1H,d,J=7.5Hz) 9.76 (1H,s)     8.27 (1H,d,J=7.5Hz) compound)   8.43 (1H,d,J=7.5Hz)    9.90 (1H,s)     Elementary analysis Molecular formula Calc. (C, H, N) % Found (C, H, N)     %  Example No. 104 106 106 109      ##STR193##      ##STR194##      ##STR195##      ##STR196##      R (D-Xyl) (L-Xyl) (D-Xyl) (L-5d Ara)       X.sup.- AcO AcO AcO Cl       Crystalline form Orange needle crystal Amorphous dark brown powder     Amorphous dark brown powder Amorphous dark red powder  (m.p. 225-229.degr     ee. C.) Specific rotatory Water-insoluble, +250° (C = 0.17)     -240° (C = 0.16) +290 (λ = 321 nm) power [α].sub.D     (impossible to determine)   +180 (λ = 259 nm)     -180 (λ     = 231 nm) Infrared absorption 3150, 1650, 1620, 1590, 1420, 3300, 1640,     1580, 1410, 1190, 3300, 1640, 1580, 1410, 1190, 3250, 1590, 1470, 1420,     1210, (KBr, cm.sup.-1) 1300, 1220, 1090, 840 1050, 920, 810 1050, 920,     810 1050, 800 Ultraviolet 249 (Ethanol-insoluble, 210 (ε20000)     210 (ε20000) 218 (ε24000) absorption 268 impossible to     determine) 227 (ε15000) 227 (ε15000) 268 (ε18000)      (λ.sub.max.sup.EtOH, nm) 281 250 (ε24000) 250 (ε2     4000) 281 (ε17000)  323 270 (ε26000) 270 (ε26000)      322 (ε27000)   325 (ε48000) 325 (ε48000) Mass     spectrum (C.I.) 395 395 395 379 (SIMS, m/z) [C.sub.22 H.sub.23 N.sub.2     O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22     H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.4     ].sup.+ Proton NMR Impossible to determine   1.58 (3H,d,J=6.5Hz) 2.85     (DMSO-d.sub.6, δ in ppm, (insoluble in DMSO-d.sub.6)   (3H,s) 3.30     (3H,s) 3.88 CD.sub.2 HSOCD.sub.3 proton    (1H,m) 4.18 (1H,m) 4.41     (1H,m) chemical shift (δ    5.74 (1H,d) 5.84 (1H,d) 2.50) was used     as    6.60 (1H,d,J=5Hz,1'-H) internal standard,    7.18 (1H,dd,J=2,9Hz)     Intensity of NMR    7.54 (1H,d,J=9Hz) magnetic field was    7.85     (1H,d,J=2Hz) 8.39 (1H, indicated in each    d,J=7.5Hz) 8.45 (1H,d,     compound)    7.5Hz) 9.43 (1H,s) 9.91 (1H,s)     12.01 (1H,s) Elementary     analysis C.sub.24 H.sub.26 N.sub.2 O.sub.7.H.sub.2 O Molecular formula     61.01, 5.97, 5.93  61.32, 5.68, 5.97 Calc. (C, H, N) % Found (C, H, N)     %   Example No. 110 111 112      ##STR197##      ##STR198##      ##STR199##      R (D-Ara) (L-Ara)       X.sup.- Br Br CH.sub.3      CO.sub.2.sup.-                                    Crystalline form     Amorphous dark red powder Amorphous dark red powder Amorphous red powder     Specific rotatory -820 (λ = 319 nm) +740 (λ = 319 nm)     -240° (C = 0.11 1% CF.sub.3 COOH/H.sub.2 O) power [α].sub.D     -610 (λ = 262 nm) +560 (λ = 256 nm)  +360 (λ = 230     nm) -580 (λ = 218 nm) Infrared absorption 3270, 1600, 1480, 1420,     1290, 3270, 1600, 1480, 1420, 1290, 3200, 1635, 1590, 1560, 1470, (KBr,     cm.sup.-1) 1220, 1120, 1060, 820 1220, 1120, 1060, 820 1400, 1210, 1190     Ultraviolet 212 (ε24000) 212 (ε24000) 207 (ε20000     ) absorption 251 (ε20000) 261 (ε20000) 226 (ε1300     0) (λ.sub.max.sup.EtOH, nm) 266 (ε21000) 266 (ε210     00) 268 (ε22000)  281 (ε19000) 281 (ε19000) 280     (ε20000)  322 (ε42000) 322 (ε42000) 324 (.epsilon     .45000) Mass spectrum 395 395 425 (SIMS, m/z) [C.sub.22 H.sub.23 N.sub.2     O.sub.5 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.5 ].sup.+ [C.sub.23     H.sub.25 O.sub.6 N.sub.2 ].sup.+ Proton NMR 2.85 (3H,s) 3.30 (3H,s) Same     as in left 1.68 (3H,s) 2.80 (3H,s) 3.24 (DMSO-d.sub.6, δ in ppm,     3.84 (1H,m) 3.95 (1H,m)  (3H,s) 5.85 (1H,d,J=8.5Hz CD.sub.2 HSOCD.sub.3     proton 4.04 (1H,m) 4.16 (1H,m)  1'-H) 7.16 (1H,dd,J=2,9Hz) chemical     shift (δ 4.53 (1H,m) 5.69 (2H,m)  7.53 (1H,d,J=9Hz) 7.82 (1H,d,     2.50) was used as 5.93 (1H,d)  J=2Hz) 8.36 (1H,d,J=7.5Hz) internal     standard, 6.55 (1H,d,J=6Hz,1'-H)  8.51 (1H,d,J=7.5Hz) 9.97 (1H,s)     Intensity of NMR 7.17 (1H,dd,J=2,9Hz)  (360MHz) magnetic field was 7.54     (1H,d,J=9Hz) indicated in each 7.84 (1H,d,J=2Hz) compound) 8.46 (1H,d,J=7     .5Hz)  8.54 (1H,d,J=7.5Hz)  9.43 (1H,s) 10.20 (1H,s)  11.98 (1H,s)     Elementary analysis   C.sub.25 H.sub.28 N.sub.2 O.sub.8 Molecular     formula   61.97, 5.83, 5.78 Calc. (C, H, N) %   62.03, 5.73, 5.59 Found     (C, H, N) %

    TABLE 2      Example No. 113 113 114 114 115       R.sup.2      ##STR200##      ##STR201##      ##STR202##      ##STR203##      ##STR204##       R.sup.1 OA.sub.C OA.sub.C OA.sub.C OA.sub.C OA.sub.C R.sup.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 X.sup.- Cl.sup.- Cl.sup.- Br.sup.-     Br.sup.- Br.sup.- Crystalline form Amorphous orange powder Amorphous     orange powder Amorphous red powder Amorphous red powder Amorphous orange     powder Specific (27° C.) (27° C.) (27°      C.) (27° C.) (27°      C.) rotatory [α].sub.D -71° (C=0.14,MeOH) +76°     (C=0.13, MeOH) -196° (C=0.15,MeOH) +190° (C=0.12,MeOH)     +184° (C=0.12,MeOH) power Infrared absorption 1730, 1635, 1600,     1590, 1560, 1730, 1635, 1600, 1590, 1560, 1740, 1645, 1610, 1600, 1595,     1740, 1645, 1610, 1600, 1595, 1720, 1630, 1580, 1560, 1460, (KBr,     cm.sup.-1) 1470, 1400, 1250, 1200, 1090, 1470, 1400, 1250, 1200, 1090,     1480, 1460, 1410, 1380, 1280, 1480, 1460, 1410, 1380, 1280, 1390, 1260,     1190, 1090, 800  701 710 1210, 1110, 1080, 810 1210, 1110, 1080, 810 705     Ultraviolet 233 (ε52000) 320 (ε63000) 233 (ε52000     ) 320 (ε63000) 201 (ε60000) 278 (ε(26000) 201     (ε60000) 278 (ε26000) 201 (ε56000) 280 (ε     28000) absorption 258 (ε26000) 258 (ε26000) 230 (.epsilon     .59000) 320 (ε61000) 230 (ε59000) 320 (ε61000)     232 (ε57000) 319 (ε72000) (λ .sub.max.sup. EtOH,     nm) 278 (ε24000) 278 (ε24000) 258 (ε28000) 258     (ε28000) 257 (ε31000) Mass spectrum 763 763 763 763 763     (SIMS, m/z) [C.sub.46 H.sub.39 N.sub.2 O.sub.9 ].sup.+ [C.sub.46     H.sub.39 N.sub.2 O.sub.9 ].sup.+ [C.sub.46 H.sub.39 N.sub.2 O.sub.9     ].sup.+ [C.sub.46 H.sub.39 N.sub.2 O.sub.9 ].sup.+ [C.sub.46 H.sub.39     N.sub.2 O.sub.9 ].sup.+ Proton NMR 2.36 (3H,S) 3.15 (3H,S) Same as in     the left 2.36 (3H,S) 3.16 (3H,S) Same as in the left 2.36 (3H,S) 3.20     (3H,S) (DMSOd.sub.6, δ in ppm, 4.31 (3H,S) 4.95 (1H,dd)  3.24     (3H,S) 4.33 (3H,S)  3.28 (3H,S) 4.34 (3H,S) CD.sub.2 HSOCD.sub.3 proton     5.13 (1H,dd) 5.42 (1H,quintet)  4.97 (2H,brd) 5.18 (1H,q,J=5Hz)  4.86     (2H,m) 5.74 (1H,m) chemical shift (δ 2.50) 6.10 (1H,dd) 6.14     (1H,S)  6.11 (1H,t,J=5Hz)  6.01 (1H,t) 6.25 (1H,t) was used as internal     7.05 (1H,S,1'-H)  6.20 (1H,t,J=5Hz)  7.21 (1H,d,J=1.5Hz,1'-H) standard,     Intensity of 7.32-8.25 (18H,m)  7.05 (1H,d,J=5Hz,1'-H)  7.30-8.15     (17H,m) NMR magnetic field was 8.68 (1H,d,J=7.5Hz)  7.44-8.03 (17H,m)     8.26 (1H,d,J=2Hz) indicated in each 8.82 (1H,d,J=7.5Hz)  8.24 (1H,d,J=2Hz     )  8.72 (1H,d,J=7.5Hz) compound) 10.21 (1H,S)  8.65 (1H,d,J=8Hz)  8.83     (1H,d,J=7.5Hz)  (270 MHz)  8.77 (1H,d,J=8Hz)  10.16 (1H,S)    10.26     (1H,S)  (360) MHz)    (270 MHz) Elementary analysis Molecular formula     C.sub.46 H.sub.39 N.sub.2 O.sub.9 Cl.3H.sub.2 O C.sub.46 H.sub.39     N.sub.2 O.sub.9 Cl.3H.sub.2 O C.sub.46 H.sub.39 N.sub.2 O.sub.9      Br.1.5H.sub.2 O C.sub.46 H.sub.39 N.sub.2 O.sub.9 Br.1.5H.sub.2 O Calc.     (C, H, N) % 64.75, 5.32, 3.28 64.75, 5.32, 3.28 63.45, 4.86, 3.22 63.45,     4.86, 3.22 -- Found (C, H, N) % 64.51, 5.21, 3.35 64.59, 5.35, 3.29     63.62, 4.73, 3.23 63.51, 4.92, 3.25       Example No. 115 116 117 117 118       R.sup.2      ##STR205##      ##STR206##      ##STR207##      ##STR208##      ##STR209##       R.sup.1 OA.sub.C OA.sub.C OA.sub.C OA.sub.C OA.sub.C R.sup.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 X.sup.- Br.sup.- Cl.sup.- Cl Cl     Cl.sup.- Crystalline form Amorphous orange powder Amorphous orange     powder Amorphous orange powder Amorphous orange powder Amorphous red     powder Specific (27° C.) (28° C.) -224° (C=0.16,     CH.sub.3 OH) +230° (C=0.19, CH.sub.3 OH) -105° (C=0.11,     CH.sub.3 OH) rotatory [α].sub.D -177  (C=0.15,MeOH) -298°     (C=0.10,MeOH) power Infrared absorption 1720, 1630, 1580, 1560, 1460,     1725, 1630, 1580, 1560, 1460, 1730, 1630, 1585, 1560, 1470, 1730, 1630,     1585, 1560, 1470, 1730, 1630, 1600, 1580, 1470, (KBr, cm.sup.-1) 1390,     1260, 1190, 1090, 800, 1395, 1250, 1200, 1100, 920, 1395, 1310, 1275,     1200, 1090 1395, 1310, 1275, 1200, 1090, 1450, 1400, 1385, 1370, 1270,     705 800, 710  920 1210, 1120, 1100 Ultraviolet 201 (ε56000) 280     (ε28000) 201 (ε38000) 280 (ε22000) 201 (ε     42000) 280 (ε24000) 201 (ε41000), 280 (ε24000)     201 (ε45000) 277 (ε35000) absorption 232 (ε57000)      319 (ε72000) 232 (ε40000) 318 (ε59000) 230     (ε38000) 319 (ε61000) 230 (ε38000, 319 (ε     61000) 231 (ε40000) 319 (ε61000) (λ .sub.max.sup.     EtOH, nm) 257 (ε31000) 257 (ε25000) 258 (ε27000)     258 (ε27000) 258 (ε36000) Mass spectrum 763 643 629.sup.+      629.sup.+ 643 (SIMS, m/z) [C.sub.46 H.sub.39 N.sub.2 O.sub.9 ].sup.+     [C.sub.39 H.sub.35 N.sub.2 O.sub.7 ].sup.+ [C.sub.38 H.sub.33 N.sub.2     O.sub.7 ].sup.+ [C.sub.38 H.sub.33 N.sub.2 O.sub.7 ].sup.+ [C.sub.39     H.sub.35 N.sub.2 O.sub.7 ].sup.+ Proton NMR 2.36 (3H,S) 3.20 (3H,S) 1.68     (3H,d,J= 6.5Hz) 2.36 (3H,S) 3.15 (3H,S) Same as in the left 1.76     (3H,d,J=6.5 Hz) (DMSOd.sub.6, δ in ppm, 3.28 (3H,S) 4.34 (3H,S)     2.36 (3H,S) 3.18 (3H,S) 3.26 (3H,S) 4.28 (3H,S)  2.36 (3H,S) 3.20 (3H,S)     CD.sub.2 HSOCD.sub.3 proton 4.86 (2H,m) 5.74 (1H,m) 3.23 (3H, S) 4.33     (3H,S) 4.60 (1H,d,J=10.6Hz)  4.34 (3H,S) 4.82 (1H,m) chemical shift     (δ 2.50) 6.01 (1H,t) 6.25 (1H,t) 5.43 (1H,q) 5.60 (1H,S) 5.22     (1H,dd,J=3.3,10.6Hz)  5.75 (1H,t,J=5Hz) was used as internal 7.21     (1H,d,J=1.5Hz,1'-H) 6.12 (1H,S) 7.16 (1H,S,1'-H) 6.08 (1H,t) 6.29 (1H,t,      6.15 (1H,t,J=5Hz) standard, Intensity of 7.30-8.15 (17H,m) 7.19-8.16     (12H,m) J=5Hz) 7.02 (1H,d,J=6Hz)  6.94 (1H,d,J=5Hz) NMR magnetic field     was 8.26 (1H,d,J=2Hz) 8.23 (1H,d,J=2Hz) 7.39-8.10 (12H,m)  7.41-8.03     (12H,m) indicated in each 8.72 (1H,d,J=7.5Hz) 8.70 (1H,d,J=7.9Hz) 8.23     (1H,d,J=2Hz)  8.28 (1H,d,J=2Hz) compound) 8.83 (1H,d,J=7.5Hz) 8.75     (1H,d,J=7.9Hz) 8.70 (1H,d,J=7.5Hz)  8.74 (1H,d,J=7.5Hz)  10.16 (1H,S)     10.08 (1H,S) 8.85 (1H,d,J=7.5Hz)  8.78 (1H,d,J=7.5Hz)  (360 MHz) (270     MHz) 10.30 (1H,S)  10.28 (1H,S) Elementary analysis Moleucular formula     C.sub.38 H.sub.33 N.sub. 2 O.sub.7 Cl.2.5H.sub.2 O C.sub.38 H.sub.33     N.sub.2 O.sub.7 Cl.2.5H.sub.2 O Calc. (C, H, N) % -- -- 64.27, 5.39,     3.94 64.27, 5.39, 3.94 -- Found (C, H, N) %   64.49, 5.10, 4.08 64.15,     5.40, 3.98       Example No. 119 119 120 120 121       R.sup.2      ##STR210##      ##STR211##      ##STR212##      ##STR213##      ##STR214##       R.sup.1 OA.sub.C OA.sub.C OH OH OH R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 CH.sub.3 X.sup.- Br.sup.- Br.sup.- Cl.sup. - Cl.sup.- Br.sup.-     Crystalline form Amorphous orange powder Amorphous orange powder     Amorphous orange powder Amorphous orange powder Amorphous orange powder     Specific +35° (C=0.11, CH.sub.3 OH) -34° (C=0.12, CH.sub.3     OH) (28° C.) (28° C.) (28°      C.) rotatory [α].sub.D   +175° (C=0.05, DMSO) -168°     (C=0.07, DMSO) -118° (C=0.5,DMSO) power Infrared absorption 1755,     1630, 1580, 1465, 1390, 1755, 1630, 1580, 1465, 1390 3250, 2930, 1640,     1585, 1560, 3250, 2930, 1640, 1585, 1560, 1640, 1580, 1480, 1450, 1400,     (KBr, cm.sup.-1) 1370, 1290, 1250, 1200, 1090 1370, 1290, 1250, 1200,     1090 1470, 1395, 1290, 1220, 1100, 1470, 1395, 1290, 1220, 1100, 1290,     1245, 1220, 1150, 1110,    1050, 900, 810, 750 1050, 900, 810, 750 1090,     1040, 900, 860, 810, 800,      3250 Ultraviolet 206 (ε40000) 318     (ε62000) 206 (ε40000) 318 (ε62000) 211 (ε     24000) 284 (ε26000) 211 (ε24000) 284 (ε26000)     210 (ε24000) 284 (ε25000) absorption 257 (ε25000)      257 (ε25000) 227 (ε17000) 327 (ε49000) 227     (ε17000) 327 (ε49000) 227 (ε17000) 327 (ε     51000)  (λ .sub.max.sup. EtOH, nm) 280 (ε21000) 280     (ε21000) 220 (ε29000) 220 (ε29000) 270 (ε     30000)  Mass spectrum 721 721 409 409 409 (SIMS, m/z) [C.sub.46 H.sub.45     N.sub.2 O.sub.6 ].sup.+ [C.sub.46 H.sub.45 N.sub.2 O.sub.6 ].sup.+     [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2     O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ Proton NMR     2.37 (3H,S) 3.11 (3H,S) Same as in the left Same as in the right 3.05     (3H,S) 3.18 (3H,S) 4.17 3.11 (3H,S) 3.24 (3H,S) (DMSOd.sub.6, δ in     ppm, 3.17 (3H,S) 3.91 (2H,m)   (3H,S) 3.97 (2H,m), 4.17 (1H,S) 3.81     (1H,brd,J=12Hz) CD.sub.2 HSOCD.sub.3 proton 4.30 (3H,S) 4.34-4.79   4.34     (1H,S), 4.49 (1H,q), 5.11 3.91 (1H,brd,J=12Hz) chemical shift (δ     2.50) (10H,m) 6.85 (3H,m)   (1H,t,J=3.5Hz) 5.73 (1H,S) 4.23 (3H,S)     4.23-4.29 (2H,m) was used as internal 7.03 (3H,m) 7.36-7.41 (9H,m)     6.37 (1H,d,J=3Hz) 6.33 4.34 (1H,m) 5.49 (1H,brs) standard, Intensity of     7.53 (1H,dd,J=2,9Hz)   (1H,S,1'-H) 7.20 (1H,dd, 5.64 (1H,brs) 5.90     (1H,brs) NMR magnetic field was 7.87 (1H,d,J=9Hz)   J=2,9Hz) 7.59     (1H,d,J=9Hz) 6.28 (1H,d,J=4.5Hz,1'-H) indicated in each 8.23 (1H,d,J=2Hz)        7.81 (1H,d,J=2Hz) 8.55 (1H,d, 7.22 (1H,dd,J=2Hz,9Hz) compound) 8.34     (1H,d,J=7.5Hz)   J=7.5Hz) 8.63 (1H,d,J=7.5Hz) 7.64 (1H,d,J=9Hz) 7.84     (1H,d,  8.62 (1H,d,J=7.5Hz)   9.53 (1H,S) 10.10 (1H,S) J=2Hz) 8.61     (1H,d,J=7Hz)  10.06 (1H,S)    8.65 (1H,d,J=7Hz) 9.56      (1H,brs) 10.25     (1H,S) [360 MHz] Elementary analysis Molecular formula   C.sub.23     H.sub.25 N.sub.2 O.sub.5 Cl.H.sub.2 O C.sub.23 H.sub.25 N.sub.2 O.sub.5     Cl.H.sub.2 O C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br Calc. (C, H, N) % --     -- 59.68, 5.88, 6.05 59.68, 5.88, 6.05 56.45, 5.15, 5.72 Found (C, H, N)     %   59.52, 5.81, 6.09 59.37, 5.65, 5.96 56.26, 5.12, 5.67       Example No. 121 122 122 123 124       R.sup.2      ##STR215##      ##STR216##      ##STR217##      ##STR218##      ##STR219##       R.sup.1 OH OH OH OH OH R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 X.sup.- Br.sup.- Br.sup.- Br.sup.- Cl.sup.- Cl.sup.- Crystalline      form Amorphous orange powder Amorphous orange powder Amorphous orange     powder Amorphous orange powder Amorphous orange powder Specific (28.degre     e. C.) (28° C.) (28° C.) (28° C.) +100°     (C=0.02, DMSO) rotatory [α].sub.D +123° (C=0.06, DMSO)     +48° (C=0.08, DMSO) -44° (C=0.8, DMSO) -49° (C=0.6,     DMSO) power Infrared absorption 1640, 1580, 1480, 1450, 1400, 3250,     1630, 1580, 1560, 1470, 3250, 1630, 1580, 1560, 1470, 3250, 1630, 1585,     1560, 1475, 3300, 1630, 1580, 1560, 1465 (KBR, cm.sup.-1) 1290, 1245,     1220, 1150, 1110, 1390, 1220, 1090, 1060, 1040, 1390, 1220, 1090, 1060,     1040, 1400, 1230, 1100, 1050, 900, 1400, 1380, 1220, 1085, 1045  1090,     1040, 900, 860, 810, 895, 795, 740 895, 795, 740 800, 750  800, 3250     Ultraviolet 210 (ε24000) 284 (ε25000) 210 (ε24000     ) 284 (ε25000) 210 (ε24000) 284 (ε25000) 211     (ε20000) 283 (ε21000) 210 (ε23000) 284 (ε     24000) absorption 227 (ε17000) 327 (ε51000) 227 (.epsilon     .17000) 327 (ε49000) 227 (ε17000) 327 (ε49000)     228 (ε14000) 327 (ε42000) 227 (ε16000) 328     (ε45000) (λ .sub.max.sup. EtOH, nm) 270 (ε30000)     270 (ε 29000) 270 (ε29000) 270 (ε25000) 270     (ε29000) Mass spectrum 409 409 409 393 379 (SIMS, m/z) [C.sub.23     H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5     ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub. 23 H.sub.25     N.sub.2 O.sub.4 ].sup.+ [C.sub.22 H.sub.23 N.sub.2 O.sub.4 ].sup.+     Proton NMR 3.11 (3H,S) 3.24 (3H,S) 3.12 (3H,S) 3.27 (3H,S) 3.70 Same as     in the left 1.44 (3H,d,J=6.5Hz) 3.12 (3H,S) 3.26 (3H,S) (DMSOd.sub.6,     δ in ppm, 3.81 (1H,brd,J=12Hz) (2H,m) 4.16 (1H,q) 4.37 (1H,q)     3.10 (3H,S) 3.25 (3H,S) 4.09 (1H,d) 4.28 (1H,m) CD.sub.2 HSOCD.sub.3     proton 3.91 (1H,brd),J=12Hz) 4.59 (1H,q) 4.23 (3H,S) 5.20  3.92 (1H,t)     4.20 (3H,S) 4.45 (1H,m) 4.72 (1H,dd) chemical shift (δ 2.50 4.23     (3H,S) 4.23-4.29 (2H,m) (1H,t) 5.69 (1H,d) 6.18 (1H,d)  4.36 (1H,brs)     4.72 (1H,m) 4.23 (3H,S) 5.58 (1H,d) was used as internal 4.34 (1H,m)     5.49 (1H,brs) 6.37 (1H,d,J=3Hz,1'-H) 7.22  5.73 (1H,d) 6.35 (1H,brs)     5.93 (1H,d) 6.27 (1H,d,J=7Hz, standard, Intensity of 5.64 (1H,brs) 5.90     (1H,brs) (1H,dd,J=2,9Hz) 7.65 (1H,d  6.42 (1H,d,J=2.5Hz,1'-H) 1'-H) 7.23     (1H,dd,J=2,9Hz) NMR magnetic field was 6.28 (1H,d,J=4.5Hz,1'-H) J=9Hz)     7.87 (1H,d,J=2Hz)  7.22 (1H,dd,J=2,9Hz) 7.63 7.65 (1H,d,J=9Hz) 7.87 (1H,     indicated in each 7.22 (1H,dd,J=2Hz,9Hz) 8.58 (2H,S)  1H,d,J=9Hz) 7.86     (1H,d, d,J=2Hz) 8,54 (1H,d,J=7.5Hz) compound) 7.64 (1H,d,J=9Hz) 7.84     (1H,d, 9.53 (1H,S) 9.97 (1H,S)  J=2Hz) 8.57 (2H,S) 8.58 (1H,d,J=7.5Hz)     J=2Hz) 8.61 (1H,d,J=7Hz) (360 MHz)  9.58 (1H,brs) 9.98 (1H,S) 9.58     (1H,S) 10.01 (1H,S)  8.65 (1H,d,J=7Hz) 9.56   (360 MHz)  (1H,brs) 10.25     (1H,S) [360 MHz] Elementary analysis Molecular formula C.sub.23 H.sub.25     N.sub.2 O.sub.5 Br C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br.H.sub.2 O     C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br.H.sub.2 O Calc. (C, H, N) % 56.45,     5.15, 5.72 54.44, 5.36, 5.52 54.44, 5.36, 5.52 -- -- Found (C, H, N) %     56.53, 5.21 5.68 54.35, 4.98, 5.38 54.46, 5.21, 5.63      Example No. 124 125 126 126 127     R.sup.2      ##STR220##      ##STR221##      ##STR222##      ##STR223##      ##STR224##       R.sup.1 OH OH OH OH OA.sub.C R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 CH.sub.3 X.sup.- Cl.sup.- Cl.sup.- Br.sup.- Br.sup.- Cl.sup.-     Crystalline form Amorphous orange powder Amorphous red powder Amorphous     dark red powder Amorphous dark red powder Amorphous reddish orange     powder Specific -98° (C=0.03, DMSO) -40° (C=0.04, DMSO)     Poor permeability Not determinable (28°) rotatory [α].sub.D         +176° (C=0.14, MeOH) power Infrared absorption 3300, 1630,     1580, 1560, 1465 3200, 1630, 1585, 1560, 1470 3350, 1630, 1590, 1560,     1470 3350, 1630, 1590, 1560, 1470 1730, 1630, 1595, 1585, 1470, (KBr,     cm.sup.-1) 1400, 1380, 1220, 1085, 1045 1450, 1395, 1220, 1090, 1020     1400, 1290, 1065, 800 1400, 1290 1450, 1395, 1270, 1200, 1090,  800     705 Ultraviolet 210 (ε23000) 284 (ε24000) 212 (ε2     0000) 286 (ε21000) 215 (ε25000) 215 (ε25000) 283     (ε22000) 201 (ε48000) 278 (ε26000) absorption     227 (ε16000) 328 (ε45000) 228 (ε15000) 328     (ε42000) 283 (ε22000) 324 (ε24000) 324 (ε     24000) 230 (ε53000) 319 (ε65000) (λ .sub.max.sup.     EtOH, nm) 270 (ε29000) 272 (ε25000)   257 (ε28000     ) Mass spectrum 379 393 409 409 763 (SIMS, m/z) [C.sub.22 H.sub.23     N.sub.2 O.sub.4 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.4 ].sup.+     [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2     O.sub.5 ].sup.+ [C.sub.46 H.sub.39 N.sub.2 O.sub.9 ].sup.+ Proton NMR     3.12 (3H,S) 3.26 (3H,S) 1.53 (3H,d,J=6.5Hz) 3.13 (3H,S) 3.84 (1H,m) 3.13     (3H,S) 3.84 (1H,m) α     Form 2.36 (3H,S) 3.18 (DMSOd.sub.6, δ in ppm, 4.09 (1H,d) 4.28     (1H,m) 3.11 (3H,S) 3.25 (3H,S) 3.96 (1H,m) 4.04 (1H,m) 3.96 (1H,m) 4.04     (1H,m) (3H,S) 4.33 (3H,S) 4.82 (2H,m) CD.sub.2 HSOCD.sub.3 proton 4.45     (1H,m) 4.72 (1H,dd) 3.96 (1H,q,J=4Hz) 4.33 (1H,dq, 4.16 (1H,m) 4.53     (1H,m) 4.16 (1H,m) 4.53 (1H,m) 5.80 (1H,m) 6.27 (1H,t) 6.42 chemical     shift (δ 2.50) 4.23 (3H,S) 5.58 (1H,d) J=4,6.5Hz) 4.40 (1H,m) 4.24     (3H,S) 5.70 (2H,d) 4.24 (3H,S) 5.70 (2H,d) (1H,dd) 7.36-8.11 (17H,m)     7.87 was used as internal 5.93 (1H,d) 6.27 (1H,d,J=7Hz, 5.52 (1H,d,J=4Hz)      5.94 (1H,m) 5.95 (1H,d), 6.56 (1H,d, 5.95 (1H,d), 6.56 (1H,d, (1H,d,J=9H     z) 8.26 (1H,d,J=2Hz) standard, Intensity of 1'-H) 7.23 (1H,dd,J=2,9Hz),     6.28 (1H,d,J=5Hz,1'-H) J=6Hz,1'-H) 7.23 (1H,dd, J=6Hz,1'-H) 7.23 (1H,dd,     8.75 (1H,d,J=7.5Hz) 8.93 (1H, NMR magnetic field was 7.65 (1H,d,J=9Hz)     7.87 (1H, 7.22 (1H,dd,J=2,9Hz) J=2,9Hz) 7.66 (1H,d,J=9Hz) J=2,9Hz) 7.66     (1H,d,J=9Hz) d,J=7.5Hz) 10.33 (1H,S) indicated in each d,J=2Hz) 8.54     (1H,d,J=7.5Hz) 7.54 (1H,d,J=9Hz) 7.76 (1H,d, 7.87 (1H,d,J=2Hz) 7.87     (1H,d,J=2Hz) β     Form 2.34 (3H,S) 3.04 compound) 8.58 (1H,d,J=7.5Hz) J=2Hz) 8.43 (1H,d,J=7     .5Hz) 8.56 (2H,ABq) 8.56 (2H,ABq) (3H,S) 5.01 (1H,dd) 5.25  9.58 (1H,S)     10.01 (1H,S) 8.58 (1H,d,J=7.5Hz) 9.52 (1H,S), 10.22 (1H,S) 9.52 (1H,S),     10.22 (1H,S) (1H,dd) 5.36 (1H,m) 6.09   9.60 (1HbrS) 9.98 (1H,S)     (1H,dd) 6.51 (1H,dd) 7.10-8.05      (18H,m) 8.18 (1H,d,J=2Hz) 8.64     (1H,d,J=7.5Hz) 8.98 (1H,d,      J=7.5Hz) 10.23 (1H,S) Elementary     analysis Molecular formula     C.sub.46 H.sub.39 N.sub.2 O.sub.9     Cl.2H.sub.2 O Calc.(C, H, N) %     66.14, 5.19, 3.35 Found (C, H, N) %       65.90, 4.88, 3.48       Example No. 128 129 130 131 132       R.sup.2      ##STR225##      ##STR226##      ##STR227##      ##STR228##      ##STR229##       R.sup.1 OA.sub.C OH OH OA.sub.C OA.sub.C R.sup.3 CH.sub.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 X.sup.- Cl.sup.- Cl.sup.- Cl.sup.- Br.sup.-     Br.sup.- Crystalline form Amorphous reddish orange powder Amorphous     reddish orange powder Amorphous orange powder Amorphous red powder     Amorphous red powder Specific (28° C.) (28°      C.) (28° C.) (27° C.) (27°      C.) rotatory [α].sub.D -168° (C=0.11, MeOH) -17°     (C=0.06, DMSO) +16° (C=0.04, DMSO) +3° (C=0.11, MeOH)     -3° (C=0.11, MeOH) power Infrared absorption 1730, 1650, 1595,     1585, 1470, 3250, 1630, 1595, 1560, 1470, 3250, 1630, 1595, 1560, 1470,     1750, 1635, 1590, 1480, 1470, 1750, 1635, 1590, 1480, 1470, (KBr,     cm.sup.-1) 1450, 1395, 1270, 1200, 1090, 1440, 1400, 1220, 1140, 1100,     1440, 1400, 1220, 1140, 1100, 1400, 1370, 1295, 1200, 1100, 1400, 1370,     1295, 1210, 1100,  705 1050, 805, 750 1050, 805, 750 1070, 1040, 940,     890, 810 1070, 1040, 940, 890, 810 Ultraviolet 201 (ε48000) 270     (ε26000) 211 (ε28000) 284 (ε30000) 211 (ε     28000) 284 (ε30000) 209 (ε20000) 283 (ε21000)     209 (ε20000) 284 (ε21000) absorption 230 (ε53000)      319 (ε65000) 227 (ε20000) 328 (ε58000) 227     (ε20000) 328 (ε58000) 245 (ε21000) 320 (ε     54000) 245 (ε21000) 320 (ε54000) (λ .sub.max.sup.     EtOH, nm) 257 (ε28000) 270 (ε35000) 270 (ε35000)     258 (ε23000) 258 (ε23000) Mass spectrum 763 409 409 577     577 (SIMS, m/z) [C.sub.46 H.sub.39 N.sub.2 O.sub.9 ].sup.+ [C.sub.23     H.sub.25 N.sub.2 O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5     ].sup.+ [C.sub.31 H.sub.33 N.sub.2 O.sub.9 ].sup.+ [C.sub.31 H.sub.33     N.sub.2 O.sub.9      ].sup.+ Proton NMR α                               Form 2.36     (3H,S) 3.18 α     Form 3.08 (3H,S) 3.23 α     Form 3.08 (3H,S) 3.23 1.77, 2.05, 2.29, (each 3H, S) 1.77, 2.05, 2.29     (each 3H,S) (DMSOd.sub.6, δ in ppm, (3H,S) 4.33 (3H,S) 4.82 (2H,m)     (3H,S) 3.69 (1H,m) 3.80 (1H,m) (3H,S) 3.69 (1H,m) 3.80 (1H,m) 2.37     (3H,S) 3.17 (3H,S) 2.37 (3H,S) 3.17 (3H,S) CD.sub.2 HSOCD.sub.3 proton     5.80 (1H,m) 6.27 (1H,t) 6.42 4.19 (3H,s) 4.23 (1H,m) 4.55 4.19 (3H,S)     4.23 (1H,m) 4.55 4.06 (1H,m) 4.28 (1H,m) 4.06 (1H,m) 4.28 (1H,m)     chemical shift (δ 2.50) (1H,dd) 7.36-8.11 (17H,m) 7.87 (1H,m) 4.80     (1H,m) 4.91 (1H,t) (1H,m) 4.80 (1H,m) 4.91 (1H,t) 4.33 (3H,S) 5.54     (1H,m) 4.33 (3H,S) 5.54 (1H,m) was used as internal (1H,d,J=9Hz) 8.26     (1H,d,J=2Hz) 5.58 (1H,d) 5.96 (1H,d) 6.28 5.58 (1H,d) 5.96 (1H,d) 6.28     5.78 (1H,d,J=2Hz) 5.78 (1H,d,J=2Hz) standard, Intensity of 8.75 (1H,d,J=7     .5Hz) 8.93 (1H, (1H,d,J=7Hz,1'-H) 7.22 (1H,dd, (1H,d,J=7Hz,1'-H) 7.22     (1H,dd, 5.92 (1H,dd,J=2Hz,7Hz) 5.92 (1H,dd,J=2Hz,7Hz) NMR magnetic field     was d,J=7.5Hz) 10.33 (1H,S) J=2,9Hz) 7.62 (1H,d,J=9Hz) J=2,9Hz) 7.62     (1H,d,J=9Hz) 6.48 (1H,d,J=7Hz,1'-H) 6.48 (1H,d,J=7Hz,1'-H) indicated in     each β     Form 2.34 (3H,S) 3.04 7.84 (1H,d,J=2Hz) 8.56 (2H,ABq) 7.84 (1H,d,J=2Hz)     8.56 (2H,ABq) 7.56 (1H,dd,J=2Hz,9Hz) 7.56 (1H,dd,J=2Hz,9Hz) compound)     (3H,S) 5.01 (1H,dd) 5.25 9.59 (1H,S) 9.98 (1H,S) 9.59 (1H,S) 9.98 (1H,S)     7.91 (1H,d,J=9Hz) 7.91 (1H,d,J=9Hz)  (1H,dd) 5,36 (1H,m) 6.09 β     Form 3.05 (3H,S) 3.18 β     Form 3.05 (3H,S) 3.18 8.31 (1H,d,J=2Hz) 8.31 (1H,d,J=2Hz)  (1H,dd) 6.51     (1H,dd) 7.10-8.05 (3H,S) 3.95 (1H,m) 4.02 (1H,m) (3H,S) 3.95 (1H,m) 4.02     (1H,m) 8.70 (1H,d,J=6.5Hz) 8.70 (1H,d,J=6.5Hz)  (18H,m) 8.18 (1H,d,J=2Hz)      8.64 4.31 (1H,m) 4.74 (1H,m) 5.10 4.31 (1H,m) 4.74 (1H,m) 5.10 8.79     (1H,d,J=6.5Hz) 8.79 (1H,d,J=6.5Hz)  (1H,d,J=7.5Hz) 8.98 (1H,d, (1H,t)     5.51 (1H,d) 6.44 (1H,d, (1H,t) 5.51 (1H,d) 6.44 (1H,d, 10.29 (1H,S) 270     MHZ 10.29 (1H,S) 270 MHz  J=7.5Hz) 10.23 (1H,S) J=6.5Hz, 1'-H) 7.19     (1H,dd, J=6.5Hz,1'1'-H) 7.19 (1H,dd,   J=2,9Hz) 8.48 (2H,ABq) 9.56     J=2,9Hz) 8.48 (2H,ABq) 9.56   (1H,S) (1H,S) Elemenatry analysis Molecular      formula C.sub.49 H.sub.39 N.sub.2 O.sub.9 Cl.2H.sub.2 O C.sub.23     H.sub.25 N.sub.2 O.sub.5 Cl.1.5H.sub.2 O C.sub.23 H.sub.25 N.sub.2     O.sub.5 Cl.1.5H.sub.2 O C.sub.31 H.sub.33 N.sub.2 O.sub.9 Br.3H.sub.2 O     C.sub.31 H.sub.33 N.sub.2 O.sub.9 Br.3H.sub.2 O Calc.(C, H, N) % 66.14,     5.19, 3.35 58.54, 5.98, 5.94 58.54, 5.98, 5.94 52.33, 5.52, 3.94 52.33,     5.52, 3.94 Found (C, H, N) % 66.05, 5.03, 3.27 58.49, 5.76, 6.00 58.62,     5.82, 5.95 52.07, 5.41, 3.73 52.32, 5.65, 4.01       Example No. 133 134 135 136 137       R.sup.2      ##STR230##      ##STR231##      ##STR232##      ##STR233##      ##STR234##       R.sup.1 OA.sub.C OA.sub.C OA.sub.C OA.sub.C OA.sub.C R.sup.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 X.sup.- Br.sup.- Br.sup.- Br.sup.-     Br.sup.- Cl.sup.- Crystalline form Amorphous reddish orange powder     Amorphous reddish orange powder Amorphous red powder Amorphous orange     powder Amorphous redddish orange powder Specific (27° C.)     (27° C.) (27° C.) (27° C.) (27° C.) rotatory     [α].sub.D -14° (C=0.14, MeOH) +11° (C=0.23, MeOH)     -23° (C=0.11, MeOH) +24° (C=0.11, MeOH) -75°     (C=0.10, MeOH) power Infrared absorption 1750, 1630, 1580, 1460, 1390,     1750, 1630, 1580, 1460, 1390, 1750, 1630, 1580, 1560, 1465, 1750, 1630,     1580, 1560, 1465, 1750, 1630, 1580, 1560, 1460, (KBr, cm.sup.-1) 1360,     1240, 1210, 1070, 1050, 1360, 1240, 1210, 1070, 1050, 1370, 1210, 1045,     930, 810, 1370, 1210, 1045, 930, 810, 1390, 1365, 1210, 1050, 940,  920,     810 920, 810 750 750 810, 750 Ultraviolet 210 (ε18000) 282     (ε17000) 210 (ε18000) 282 (ε17000) 211 (ε     20000) 282 (ε22000) 209 (ε18000) 282 (ε21000)     209 (ε20000) 200 (ε22000) absorption 245 (ε16000)      321 (ε44000) 245 (ε16000) 321 (ε44000) 244     (ε21000) 321 (ε57000) 245 (ε20000) 321 (ε     54000) 245 (ε22000) 320 (ε56000) (λ .sub.max.sup.     EtOH, nm) 259 (ε19000) 259 (ε19000) 260 (ε25000)     260 (ε24000) 258 (ε24000) Mass spectrum 591 591 577 577     577 (SIMS, m/z) [C.sub.32 H.sub.35 N.sub.2 O.sub.9 ].sup.+ [C.sub.32     H.sub.35 N.sub.2 O.sub.9 ].sup.+ [C.sub.31 H.sub.33 N.sub.2 O.sub.9     ].sup.+ [C.sub.31 H.sub.33 N.sub.2 O.sub.9 ].sup.+ [C.sub.31 H.sub.33     N.sub.2 O.sub.9      ].sup.+ Proton NMR 1.26 (3H,d,J=6.5Hz) 1.26 (3H,d,J=6.5Hz) 1.79, 2.00,     2.27 (each 3H,S) 1.79, 2.00, 2.27 (each 3H,S) 1.76, 2.26, 2.28 (each     3H,S) (DMSOd.sub.6, δ in ppm, 1.79 1.99 2.30 (each 3H,S) 1.79 1.99     2.30 (each 3H,S) 2.36 (3H,S) 3.16 (3H,S) 2.36 (3H,S) 3.16 (3H,S) 2.37     (3H,S) 3.16 (3H,S) CD.sub.3 HSOCD.sub.3 proton 2.36 (3H,S) 3.17 (3H,S)     2.36 (3H,S) 3.17 (3H,S) 4.32 (3H,S) 4.34 (2H,m) 4.32 (3H,S) 4.34 (2H,m)     4.30 (2H,S) 4.32 (3H,S) chemical shift (δ 2.50) 4.34 (3H,S) 4.56     (1H,m) 4.34 (3H,S) 4.56 (1H,m) 5.44 (1H,S) 5.51 (2H, 5.44 (1H,S) 5.51     (2H, 5.05 (1H,d) 5.53 (2H,m) was used as internal 5.39- 5.54 (3H,m)     5.39-5.54 (3H,m) AB portion of ABX AB portion of ABX 6.59 (1H,d,J=9Hz,1'-     H) standard, Intensity of 6.42 (1H,d,J=9Hz,1'-H) 6.42 (1H,d,J=9Hz,1'-H)     J.sub.2',3' =10Hz,J.sub.1',3' =4Hz) J.sub.2',3' =10Hz,J.sub.1',3' =4Hz)     7.55 (1H,dd,J=2,9Hz) NMR magnetic field was 7.55 (1H,dd,J=2Hz,9Hz) 7.55     (1H,dd,J=2Hz,9Hz) 6.37 (1H, X portion of ABX, 6.37 (1H, X portion of     ABX, 7.90 (1H,d,J=9Hz) indicated in each 7.92 (1H,d,J=9Hz) 7.92 (1H,d,J=9     Hz) J.sub.1',2' =8Hz,1'-H) 7.55 (1H, J.sub.1',2' =8Hz,1'-H) 7.55 (1H,     8.29 (1H,d,J=2Hz) compound) 8.31 (1H,S) 8.31 (1H,S) dd,J=2, 9Hz) 7.90     (1H,d, dd,J=2, 9Hz) 7.90 (1H,d, 8.65 (2H,S) 10.29 (1H,S)  8.56 (1H,d,J=7.     5Hz) 8.56 (1H,d,J=7.5Hz) J=9Hz) 8.30 (1H,d,J=2Hz) J=9Hz) 8.30 (1H,d,J=2Hz     ) (270 MHz)  8.67 (1H,d,J=7.5Hz) 8.67 (1H,d,J=7.5Hz) 8.58 (1H,d,J=7.5Hz)     8.58 (1H,d,J=7.5Hz)  10.17 (1H,S) 10.17 (1H,S) 8.67 (1H,d,J=7.5Hz) 8.67     (1H,d,J=7.5Hz)  (270 MHz) (270 MHz) 10.17 (1H,S) 10.17 (1H,S)    (360     MHz) (360 MHz) Elementary analysis Molecular formula -- -- -- --     C.sub.31 H.sub.33 N.sub.2 O.sub.9 Cl.4H.sub.2 O Calc.(C, H, N) %     54.35, 6.03, 4.09 Found (C, H, N) %     54.08, 5.95, 4.12       Example No. 138 139 139 140 140       R.sup.2      ##STR235##      ##STR236##      ##STR237##      ##STR238##      ##STR239##       R.sup.1 OA.sub.C OA.sub.C OA.sub.C OA.sub.C OA.sub.C R.sup.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 X.sup.- Cl.sup.- Br.sup.- Br.sup.-     Br.sup.- Br.sup.- Crystalline form Amorphous reddish orange powder     Amorphous reddish orange powder Amorphous reddish orange powder Amorphous      reddish orange Amorphous redddish orange powder     powder Specific     (28° C.) (27° C.) (27° C.) rotatory [α].sub.D     +89° (C=0.10, MeOH) -1° (C=0.11, MeOH) +1° (C=0.13,     MeOH) -87° (C=0.13, CH.sub.3 OH) +90° (C=0.11, CH.sub.3     OH) power Infrared absorption 1750, 1630, 1580, 1560, 1460, 1755, 1630,     1585, 1560, 1470, 1755, 1630, 1585, 1560, 1470, 1760, 1630, 1585, 1560,     1480, 1760, 1630, 1585, 1560, 1480 (KBr, cm.sup.-1) 1390, 1365, 1210,     1050, 940, 1400, 1370, 1290, 1210, 1050, 1400, 1370, 1290, 1210, 1050,     1470, 1440, 1390, 1370, 1290, 1470, 1440, 1390, 1370, 1290  810, 750     920, 910, 810 930, 910, 810 1210, 1140, 1100, 1040 1210, 1140, 1100,     1040 Ultraviolet 210 (ε20000) 282 (ε20000) 210 (ε     20000) 283 (ε22000) 210 (ε20000) 283 (ε22000)     210 (ε20000) 280 (ε23000) 210 (ε20000) 280     (ε23000) absorption 244 (ε20000) 320 (ε50000)     247 (ε22000) 322 (ε57000) 247 (ε22000) 322     (ε57000) 245 (ε23000) 322 (ε59000) 245 (ε     23000) 322 (ε59000) (λ .sub.max.sup. EtOH, nm) 258     (ε22000) 260 (ε25000) 260 (ε25000) 258 (ε     26000) 258 (ε26000) Mass spectrum 577 649 649 649 649 (SIMS,     m/z) [C.sub.31 H.sub.33 N.sub.2 O.sub.9 ].sup.+ [C.sub.34 H.sub.37     N.sub.2 O.sub.11 ].sup.+ [C.sub.34 H.sub.37 N.sub.2 O.sub.11 ].sup.+     [C.sub.34 H.sub.37 N.sub.2 O.sub.11 ].sup.+ [C.sub.34 H.sub.37 N.sub.2     O.sub.11 ].sup.+ Proton NMR 1.76, 2.26, 2.28 (each 3H,S) 1.81, 1.99,     2.00, 2.291.81, 1.99, 2.00, 2.291.79, 2.01, 2.05, 2.09 1.79, 2.01, 2.05,     2.09 (DMSOd.sub.6, δ in ppm, 2.37 (3H,S) 3.16 (3H,S) (each 3H,S)     2.37 (3H,S) (each 3H,S) 2.37 (3H,S) (each 3H,S) (each 3H,S) 2.37 (3H,S)     CD.sub.2 HSOCD.sub.3 proton 4.30 (2H,m) 4.32 (3H,S) 3.18 (3H,S) 4.25     (2H,m) 3.18 (3H,S) 4.25 (2H,m) 2.37 (3H,S) 3.15 (3H,S) 3.15 (3H,S) 4.31     (3H,S) chemical shift (δ 2.50) 5.05 (1H,d) 5.53 (2H,m) 4.34 (3H,S)     4.76 (1H,m) 4.34 (3H,S) 4.76 (1H,m) 4.31 (3H,S) 4.27 (2H,m) 4.27 (2H,m)     4.43 (1H,m) was used as internal 6.59 (1H,d,J=9Hz,1'-H) 5.45-5.63 (3H,m)     5.45-5.63 (3H,m) 4.43 (1H,m) 5.56-5.60 (2H,m) 5.56-5.60 (2H,m) 5.93     (1H,m) standard, Intensity of 7.55 (1H,dd,J= 2,9Hz) 6.46 (1H,d,J=9Hz,1'-H     ) 6.46 (1H,d,J=9Hz,1'-H) 5.93 (1H,m) 6.42 (1H,d,J=8.5Hz, 6.42 (1H,d,J=8.5     Hz,1'-H) NMR magnetic field was 7.90 (1H,d,J=9Hz) 7.56 (1H,dd,J=1.3Hz,9Hz     ) 7.56 (1H,dd,J=1.3Hz,9Hz) 1'-H) 7.55 (1H,dd,J=2,8.5Hz) 7.55 (1H,dd,J=2,8     .5Hz) indicated in each 8.29 (1H,d,J=2Hz) 7.91 (1H,d,J=9Hz) 7.91     (1H,d,J=9Hz) 7.90 (1H,d,J=8.5Hz) 7.90 (1H,d,J=8.5Hz) compound) 8.65     (2H,S) 10.29 (1H,S) 8.31 (1H,d,J=1.3Hz) 8.31 (1H,d,J=1.3Hz) 8.30     (1H,d,J=2Hz) 8.30 (1H,d,J=2Hz)  (270 MHz) 8.59 (1H,d,J=8Hz) 8.59     (1H,d,J=8Hz) 8.65 (1H,d,J=7.5Hz) 8.65 (1H,d,J=7.5Hz)   8.69 (1H,d,J=8Hz)     8.69 (1H,d,J=8Hz) 8.75 (1H,d,J=7.5Hz) 8.75 (1H,d,J=7.5Hz)   10.18 (1H,S)     10.18 (1H,S) 10.24 (1H,S) 10.24 (1H,S)   (270 MHz) (270 MHz) Elementary     analysis Molecular formula C.sub.31 H.sub.33 N.sub.2 O.sub.9 Cl.4H.sub.2     O -- --  -- Calc.(C, H, N) % 54.35, 6.03, 4.09 Found (C, H, N) % 54.30,     6.01, 4.02       Example No. 141 142 143 144 145       R.sup.2      ##STR240##      ##STR241##      ##STR242##      ##STR243##      ##STR244##       R.sup.1 OA.sub.C OA.sub.C OA.sub.C OA.sub.C OH R.sup.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 X.sup. - Cl.sup.- Br.sup.- Br.sup.-     Br.sup.- Br.sup.- Crystalline form Amorphous reddish Amorphous orange     powder Amorphous reddish orange powder Amorphous reddish orange powder     Amorphous red powder  orange powder Specific -120° (C=0.16,     CH.sub.3 OH) -57° (C=0.15, CH.sub.3 OH) (27°      C.) (27° C.) (28°      C.) rotatory [α].sub.D   -81° (C=0.11, MeOH) +76°     (C=0.13, MeOH) -26° (C=0.07, DMSO) power Infrared absorption     1750, 1680, 1630, 1580, 1560 1750, 1630, 1590, 1560, 1465 1750, 1630,     1580, 1480, 1460, 1750, 1630, 1580, 1480, 1460, 1630, 1580, 1560, 1490,     1480, (KBr, cm.sup.-1) 1460, 1370, 1290, 1220, 1040 1370, 1290, 1210,     1040, 885 1390, 1370, 1240, 1210, 1040, 1390, 1370, 1240, 1210, 1040,     1440, 1400, 1300, 1180, 1090,  930, 810, 750  930, 890, 810 930, 890,     810 1050, 1035, 905, 800, 3250 Ultraviolet 210 (ε19000), 280     (ε22000) 210 (ε21000) 280 (ε23000) 209 (ε     21000) 282 (ε22000) 209 (ε21000) 282 (ε22000)     211 (ε25000) 284 (ε26000) absorption 244 (ε21000)     , 321 (ε58000) 247 (ε23000) 322 (ε55000) 245     (ε23000) 320 (ε58000) 245 (ε23000) 320 (ε     58000) 227 (ε17000) 328 (ε52000) (λ .sub.max.sup.     EtOH, nm) 258 (ε25000) 259 (ε25000) 258 (ε26000)     258 (ε26000) 270 (ε31000) Mass spectrum 648 635 577 577     409 (SIMS, m/z) [C.sub.34 H.sub.38 N.sub.3 O.sub.10 ].sup.+ [C.sub.33     H.sub.35 N.sub.2 O.sub.11 ].sup.+ [C.sub.31 H.sub.33 N.sub.2 O.sub.9     ].sup.+ [C.sub.31 H.sub.33 N.sub.2 O.sub.9 ].sup.+ [C.sub.23 H.sub.25     N.sub.2 O.sub.5 ].sup.+ Proton NMR 1.49 (3H,S) 1.98, 2.05, 2.08 1.78,     2.04, 2.08 (each 3H,S) [β     form] Same as in conpound 143 Same as in compound 146 (DMSOd.sub.6,     δ in ppm, (each 3H,S) 2.37 (3H,S) 2.37 (3H,S) 3.14 (3H,S) 1.78,     2.04, 2.07 (each 3H, S) CD.sub.2 HSOCD.sub.3 proton 3.12 (3H,S) 4.28     (3H,S) 3.69 (3H,S) 4.29 (3H,S) 2.37 (3H,S) 3.16 (3H,S) chemical shift     (δ 2.50) 4.30 (3H,m) 4.93 (1H,m) 4.90 (1H,d,J=9Hz) 5.65 (1H, 4.32     (3H,S) 3.88 (1H,m) was used as internal 5.35 (1H,t,J=9Hz) t,J=9Hz) 5.70     (1H,t,J=9Hz) 4.40 (1H,m), 5.48-5.56 (2H,m) standard, Intensity of 5.49     (1H,t,J=9Hz) 6.05 )1H,t,J=9Hz) 5.91 (1H,m) 6.32 (1H,d,J=9Hz, NMR     magnetic field was 6.30 (1H,d,J=9.9Hz,1'-H) 6.47 (1H,d,J=9Hz,1'-H) 1'-H)     7.55 (1H,dd,J=2Hz,8Hz) indicated in each 7.53 (1H,dd,J=2,9Hz) 7.55     (1H,dd,J=2,9Hz) 7.90 (1H,d,J=8Hz) 8.31 (1H,d, compound) 7.85 (1H,d,J=9Hz)      7.88 (1H,d,J=9Hz) J=2Hz) 8.66 (1H,d,J=7.5Hz)  8.27 (1H,d,J=2Hz) 8.28     (1H,d,J=2Hz) 8.73 (1H,d,J=7.5Hz) 10.23  8.47 (1H,d,J=9Hz) 8.66 (1H,d,J=7H     z) (1H,S)  8.64 (2H,ABq) 10.16 (1H,S) 8.80 (1H,d,J=7Hz) [α     form]   10.26 (1H,S) 1.96, 2.19, 2.28 (each 3H,S)    4.85 (1H,m) 5.21     (1H,m) 5.40    (1H,m) 6.63 (1H,S,1'-H)    10.14 (1H,S) 270 MHz Elementary      analysis Molecular formula C.sub.34 H.sub.38 N.sub.3 O.sub.10      Cl.3.5H.sub.2 O  C.sub.31 H.sub.33 N.sub.2 O.sub.9 Br.2.5H.sub.2 O     C.sub.31 H.sub.33 N.sub.2 O.sub.9 Br.2.5H.sub.2 O C.sub.23 H.sub.25     N.sub.2 O.sub.5 Br Calc. (C, H, N) % 54.65, 6.07, 5.62 -- 53.00, 5.45,     3.99 53.00, 5.45, 3.99 56.45, 5.15, 5.72 Found (C, H, N) % 54.82, 5.70,     5.66  53.16, 5.11, 4.05 53.05, 5.31, 3.85 56.71, 5.32, 5.69       Example No. 146 147 148 149 150       R.sup.2      ##STR245##      ##STR246##      ##STR247##      ##STR248##      ##STR249##       R.sup.1 OH OH OH OH OH R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 X.sup.- Br.sup.- Br.sup.- Br.sup.- Br Br.sup.- Crystalline form     Amorphous red powder Amorphous reddish Amorphous reddish orange powder     Amorphous orange powder Amorphous orange powder   orange powder Specific     (28° C.) (28° C.) (28° C.) (28°      C.) (28° C.) rotatory [α].sub.D +28° (C=0.07, DMSO)     -97° (C=0.07, DMSO) +89° (C=0.06, DMSO) -108°     (C=0.06, DMSO) +122° (C=0.06, DMSO) power Infrared absorption     1630, 1580, 1560, 1490, 1480 3370, 1630, 1590, 1470, 1440, 3370, 1630,     1590, 1470, 1440, 3250, 2910, 1630, 1580, 1560, 3250, 2910, 1630, 1580,     1560, (KBr, cm.sup.-1) 1440, 1300, 1180, 1090, 1050, 1400, 1220, 1200,     1140, 1120, 1400, 1220, 1200, 1140, 1120, 1480, 1400, 1230, 1180, 1150,     1480, 1400, 1230, 1180, 1150,  1035, 905, 800, 3250 1100, 1040, 1000,     900, 880, 1100, 1040, 1000, 900, 880, 1090, 900, 800, 745 1090, 900, 800       860, 820, 810, 740 860, 820, 810, 740 Ultraviolet 211 (ε25000)     284 (ε26000) 212 (ε25000) 283 (ε26000) 212     (ε25000) 282 (ε26000) 211 (ε25000) 284 (ε     25000) 211 (ε22000) 285 (ε23000) absorption 227 (.epsilon     .17000) 328 (ε52000) 227 (ε17000) 328 (ε52000)     227 (ε17000) 328 (ε52000) 227 (ε17000) 327     (ε49000) 227 (ε15000) 328 (ε46000) (λ     .sub.max.sup. EtOH, nm) 270 (ε31000) 270 (ε30000) 270     (ε30000) 270 (ε29000) 270 (ε27000) Mass spectrum     409 423 423 409 409 (SIMS, m/z) [C.sub.23 H.sub.25 N.sub.2 O.sub.5     ].sup.+ [C.sub.24 H.sub.27 N.sub.2 O.sub.5 ].sup.+ [C.sub.24 H.sub.27     N.sub.2 O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+     [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ Proton NMR 3.10 (3H,S) 3.28     (3H,S) Same as in compound 148 1.30 (3H,d,J=6.5Hz) 3.00 (3H,S) 3.25     (3H,S) Same as in the left (DMSOd.sub.6, δ in ppm, 3.84-3.88     (2H,m)  3.12 (3H,S) 3.26 (3H,S) 3.66 (1H,m) 3.91 (3H,m) CD.sub.2     HSOCD.sub.3 proton 3.91-3.97 (2H,m) 4.09 (1H,m)  3.62-3.69 (2H,m) 3.88     (1H,m) 4.10 (1H,d) 4.22 (3H,S) chemical shift (δ 2.50) 4.24 (3H,S)     5.12 (1H,d,J=6Hz)  4.04 (1H,q,J=6.5Hz) 4.77 (1H, 5.13 (1H,d) 5.25 (1H,d)     was used as internal 5.41 (1H,brd) 5.48 (1H,d)  d,J=6.5Hz), 5.20 (1H,d     5.63 (1H,d) 5.76 (1H,d,J=9Hz, standard, Intensity of 5.98 (1H,d,J=9Hz,1'-     H)  J=5.5Hz), 5.58 (1H,d,J=5Hz) 1'-H) 7.23 (1H,dd,J=2,9Hz) NMR magnetic     field was 7.22 (1H,dd,J=2Hz,9Hz)  5.81 (1H,d,J=8.5Hz,1'-H) 7.65 (1H,d,J=9     Hz) 7.86 (1H,d, indicated in each 7.65 (1H,d,J=9Hz) 7.86  7.23 (1H,dd,J=2     Hz,9Hz) J=2Hz) 8.50 (1H,d,J=7.5Hz) compound) (1H,d,J=2Hz) 8.55 (2H,S)     7.66 (1H,d,J=9Hz) 7.87 (1H,d, 8.61 (1H,d,J=7.5Hz)  9.54 (1H,brs) 10.05     (1H,S)  J=2Hz) 8.51 (1H,d,J=7.5Hz) 9.54 (1H,S) 10.02 (1H,S)  (360 MHz)     8.61 (1H,d,J=7.5 Hz) (360 MHz)    9.55 (1H,S) 10.03 (1H,S)    (360 MHz)     Elementary analysis Molecular formula C.sub.23 H.sub.25 N.sub.2 O.sub.5     Br C.sub.24 H.sub.27 N.sub.2 O.sub.5 Br C.sub.24 H.sub.27 N.sub.2     O.sub.5 Br C.sub.23 H.sub.25 N.sub.2 O.sub.5 Br.1/2H.sub.2 O C.sub.23     H.sub.25 N.sub.2 O.sub.5 Br.1/2H.sub.2 O Calc. (C, H, N) % 56.45, 5.15,     5.72 57.26, 5.41, 5.56 57.26, 5.41, 5.56 55.43, 5.26, 5.62 55.43, 5.26,     5.62 Found (C, H, N) % 56.32, 5.15, 5.68 57.58, 5.54, 5.62 57.35, 5.41,     5.52 55.64, 5.15, 5.63 55.38, 5.03, 5.59       Example No. 151 152 153 153 154       R.sup.2      ##STR250##      ##STR251##      ##STR252##      ##STR253##      ##STR254##       R.sup.1 OH OH OH OH OH R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 X.sup.- Cl.sup.- Cl.sup.- Br.sup.- Br.sup.- Br.sup.- Crystalline      form Amorphous orange powder Amorphous orange powder Amorphous reddish     orange powder Amorphous reddish orange powder Amorphous red powder     Specific (28° C.) (28° C.) (28° C.) (28° C.)     53° (C=0.06, DMSO) rotatory [α].sub.D -47° (C=0.06,     DMSO) +58° (C=0.06, DMSO) +98° (C=0.07, DMSO) -96°     (C=0.06, DMSO) power Infrared absorption 3280, 2910, 1630, 1580, 1560,     3280, 2910, 1630, 1580, 1560, 3350, 1630, 1590, 1470, 1440, 3350, 1630,     1590, 1470, 1440, 3300, 1630, 1580, 1480, 1440, (KBr, cm.sup.-1) 1480,     1400, 1225, 1185, 1125, 1480, 1400, 1225, 1185, 1125, 1400, 1220, 1200,     1180, 1140, 1400, 1220, 1200, 1180, 1140, 1400, 1380, 1370, 1350, 1320,     1105, 1080, 1050, 910, 810, 1105, 1080, 1050, 910, 810, 1120, 1090,     1050, 900, 880, 1120, 1090, 1050, 900, 880, 1310, 1290, 1220, 1200,     1100,  740 740 801, 800, 740 810, 800, 740 1070, 1040, 1010 Ultraviolet     212 (ε24000) 284 (ε25000) 211 (ε22000) 284     (ε24000) 212 (ε18000) 284 (ε19000) 212 (ε     18000) 284 (ε19000) 210 (ε24000) 284 (ε26000)     absorption 227 (ε16000) 328 (ε50000) 227 (ε16000)      328 (ε47000) 227 (ε12000) 328 (ε37000) 227     (ε12000) 328 (ε37000) 227 (ε1700) 328 (ε5     2000) (λ .sub.max.sup. EtOH, nm) 270 (ε29000) 270     (ε28000) 270 (ε22000) 270 (ε22000) 270 (ε     31000) Mass spectrum 409 409 439 439 439 (SIMS, m/z) [C.sub.23 H.sub.25     N.sub.2 O.sub.5 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+     [C.sub.24 H.sub.27 N.sub.2 O.sub.6 ].sup.+ [C.sub.24 H.sub.27 N.sub.2     O.sub.6 ].sup.+ [C.sub.24 H.sub.27 N.sub.2 O.sub.6 ].sup.+ Proton NMR     3.11 (3H,S) 3.27 (3H,S) Same as in compound 151 3.05 (3H,S) 3.18 (3H,S)     Same as in the left 3.11 (3H,S) 3.42-3.51 (2H,m) (DMSOd.sub.6, δ     in ppm, 3.75 (1H,m) 3.95 (1H,d,J=12Hz)  3.64-3.73 (3H,m) 3.87-3.95     3.57-3.71 (3H,m) 3.84 (1H,m) CD.sub.2      HSOCD.sub.3 proton 4.16 (1H,d,J=12Hz) 4.02 (2H,m)  (3H,m) 4.17 (3H,S)     4.90  4.23 (3H,S) 4.81 (1H,t,J=5.5Hz) chemcial shift (δ 2.50) 4.23     (3H,S) 5.41 (1H,d)  (1H,brs) 4.99 (1H,d,J=7Hz)  5.38 (1H,d,J=5Hz) 5.52     (1H,d was used as internal 5.51 (1H,d) 5.72 (1H,d)  5.26 (1H,d,J=5Hz)     5.66  J=4Hz) 5.72 (1H,d,J=5Hz) standard, Intensity of 6.03 (1H,d,J=     9Hz,1'-H)  (1H,brs) 5.84 (1H,d,J=8.5Hz,  5.88 (1H,d,J=9Hz,1'-H) NMR     magnetic field was 7.23 (1H,dd,J=2,9Hz)  1'-H) 7.22 (1H,dd,J=2Hz,9Hz)     7.24 (1H,dd,J=2,9Hz) indicated in each 7.88 (1H,d,J=2Hz) 8.55 (1H,d,     J=2Hz) 8.50 (1H,d,J=7.5Hz)  7.87 (1H,d,J=2Hz) compound) J=7.5Hz) 8.59     (1H,d,J=7.5Hz)  8.56 (1H,d,J=7.5Hz) 9.55  8.57 (2H,S) 9.56 (1H,brs)     9.59 (1H,brs) 10.07 (1H,S)  (1H,brs) 9.98 (1H,S) 360 MHz  10.03 (1H,S)     (360 MHz) Elementary analysis Molecular formula C.sub.23 H.sub.25     N.sub.2 O.sub.5 Cl.H.sub.2 O C.sub.23 H.sub.25 N.sub.2 O.sub.5      Cl.H.sub.2 O C.sub.24 H.sub.27 N.sub.2 O.sub.6 Br C.sub.24 H.sub.27     N.sub.2 O.sub.6 Br C.sub.24 H.sub.27 N.sub.2 O.sub.6 Br.1/2H.sub.2 O     Calc. (C, H, N) % 59.68, 5.88, 6.05 59.68, 5.88, 6.05 55.50, 5.24, 5.39     55.50, 5.24, 5.39 54.55, 5.34, 5.30 Found (C, H, N) % 59.78, 5.69, 6.07     59.46, 5.58, 6.00 55.42, 5.14, 5.34 55.21, 5.29, 5.35 54.88, 5.19,     5.27    Example No. 154 155 156 157 158       R.sup.2      ##STR255##      ##STR256##      ##STR257##      ##STR258##      ##STR259##       R.sup.1 OH OH OH OH OH R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 X.sup.- Br.sup.- Cl.sup.- Br.sup.- Br.sup.- Br.sup.- Crystalline      form Amorphous red powder Amorphous reddish Amorphous orange powder     Amorphous red powder Amorphous red powder   orange powder Specific     -58° (C=0.04, DMSO) -83° (C=0.07, DMSO) +20°     (C=0.05, DMSO) (28° C.) (28° C.) rotatory [α].sub.D       +30° (C=0.06, DMSO) -28° (C=0.05, DMSO) power Infrared     absorption 3300, 1630, 1580, 1480, 1440, 3300, 1670, 1640, 1590, 1560     3300, 1680, 1630, 1580, 1470, 1630, 1580, 1470, 1400, 1220 1630, 1580,     1470, 1400, 1220, (KBr, cm.sup.-1) 1400, 1380, 1370, 1350, 1320, 1480,     1400, 1300, 1225, 1100 1445, 1400, 1220, 1095, 800 1180, 1100, 1050,     1000, 900, 1180, 1100, 1050, 1000, 900,  1310, 1290, 1220, 1200, 1100,     1050  810, 3300 810, 3300  1070, 1040, 1010 Ultraviolet 210 (ε240     00) 284 (ε26000) 210 (ε22000) 285 (ε23000) 210     (ε27000) 284 (ε29000) 210 (ε25000) 284 (ε     26000) 210 (ε25000) 284 (ε26000) absorption 227 (.epsilon     .17000) 328 (ε52000) 228 (ε15000) 330 (ε45000)     227 (ε19000) 329 (ε56000) 227 (ε17000) 328     (ε50000) 227 (ε17000) 328 (ε50000) (λ     .sub.max.sup. EtOH, nm) 270 (ε31000) 272 (ε28000) 270     (ε34000) 270 (ε30000) 270 (ε30000) Mass spectrum     439 480 452 409 409 (SIMS, m/z) [C.sub.24 N.sub.27 N.sub.2 O.sub.6     ].sup.+ [C.sub.26 H.sub.30 N.sub.3 O.sub.6 ].sup. + [C.sub.24 H.sub.26     N.sub.3 O.sub.6 ].sup.+ [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+     [C.sub.23 H.sub.25 N.sub.2 O.sub.5 ].sup.+ Proton NMR 3.11 (3H,S)     3.42-3.51 (2H,m) 1.52 (3H,S) 3.05 (3H,S) 3.11 (3H,S) 3.49 (1H,m)     [β form] Same as in compound 157 (DMSOd.sub.6, δ in ppm,     3.57-3.71 (3H,m) 3.84 (1H,m) 3.23 (3H,S) 3.63 (4H,m) 3.70-3.77 (2H,m)     3.94 (1H,d, 3.14 (3H,S) 3.65-3.79 (3H,m) CD.sub.2 HSOCD.sub.3 proton     4.23 (3H,S) 4.81 (1H,t,J=5.5Hz) 3.88 (1H,m) 4.12 (1H,m) J=10Hz) 4.24     (3H,S) 5.52 (1H, 4.08-4.20 (2H,m) 4.27 (3H,S) chemical shift (δ     2.50) 5.38 (1H,d,J=5Hz) 5.52 (1H,d, 4.17 (3H,S) 4.89 (1H,t) d,J=5.5Hz)     5.64 (1H,d,J=4.5Hz) 5.35 (1H,d,J=5.5Hz) 5.53 (1H, was used as internal     J=4Hz) 5.72 (1H,d,J=5Hz) 5.48 (1H,d) 5.50 (1H,d) 5.78 (1H,m) 5.93     (1H,d,J=9Hz, d,J=4.5Hz) 5.71 (1H,d,J=5.5Hz) standard, Intensity of 5.88     (1H,d,J=9Hz,1'-H) 5.94 (1H,d,J=9.5Hz,1'-H) 1'-H) 7.23 (1H,dd,J=2,9Hz)     5.81 (1H,d,J=9Hz,1'-H) 7.24 NMR magnetic field was 7.24 (1H,dd,J=2,9Hz)     7.23 (1H,dd,J=2,9Hz) 7.40 (1H,S) 7.72 (1H,S) (1H,dd,J=2Hz,9Hz) 7.68     (1H,d, indicated in each 7.66 (1H,d,J=9Hz) 7.62 (1H,d,J=9Hz) 7.84 (1H,     7.66 (1H,d,J=9Hz) J=9Hz) 7.89 (1H,d,J=2Hz) 8.57 compound) 7.87 (1H,d,J=2H     z) d,J=2Hz) 8.28 (1H,d,J=9Hz) 7.87 (1H,d,J=2Hz) (2H,S) 9.54 (1H,S) 10.04     (1H,S)  8.57 (2H,S) 9.56 (1H,brs) 8.49 (1H,d,J=7.5Hz) 8.58 (1H,d,J=7.5Hz)      [α     form]  10.03 (1H,S) 8.54 (1H,d,J=7.5Hz) 8.64 (1H,d,J=7.5Hz) 4.26 (3H,S)     5.42 (1H,d,J=8Hz)   9.60 (1H,S) 9.56 (1H,brs) 10.05 (1H,S) 5.60 (1H,d,J=5     .5Hz) 5.87 (1H,     d,J=3.5Hz) 6.34 (1H,brs,1'-H)     7.67 (1H,d,J=9Hz)     9.52 (1H,S)     10.00 (1H,S) 360 MHz Elementary analysis Molecular     formula C.sub.24 H.sub.27 N.sub.2 O.sub.6 Br.1/2H.sub.2 O   C.sub.23     H.sub.25 N.sub.2 O.sub.5 Br.1/2H.sub.2 O C.sub.23 H.sub.25 N.sub.2     O.sub.5 Br.1/2H.sub.2 O Calc. (C, H, N) % 54.55, 5.34, 5.30 -- -- 55.43,     5.26, 5.62 55.43, 5.26, 5.62 Found (C, H, N) % 54.63, 5.32, 5.21     55.36, 5.14, 5.61 55.38, 5.25, 5.69       Example No. 159 160 160 161 162        R.sup.2      ##STR260##      ##STR261##      ##STR262##      ##STR263##      ##STR264##       R.sup.1 OH OH OH OH OH R.sup.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     CH.sub.3 X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.- Crystalline      form Amorphous orange powder Amorphous orange powder Amorphous orange     powder Amorphous reddish orange powder Amorphous orange powder Specific     (27° C.) (28°  C.) (28° C.) (28° C.)     (28° C.) rotatory [α].sub.D +35° (C= 0.04, MeOH)     +44° (C= 0.06, MeOH) -42° (C= 0.05, MeOH) +3° (C=     0.13, DMSO) +75° (C= 0.07, DMSO) Infrared absorption 3400, 3150,     1750, 1640, 1590, 3400, 3100, 1750, 1630, 1585, 3400, 3100, 1750, 1630,     1585, 3250, 2900, 1630, 1580, 1560, 3250, 2900, 1630, 1585, 1560, (KBr,     cm.sup.-1) 1565, 1480, 1410, 1380, 1220, 1560, 1470, 1450, 1400, 1370,     1560, 1470, 1450, 1400, 1390, 1470, 1395, 1220, 1200, 1180, 1470, 1400,     1220, 1110, 1050,  1140, 1050, 915, 810, 750 1220, 1050, 800, 745 1220,     1050 1140, 1100, 1040, 920, 800, 740 810, 750 Ultraviolet absorption 211     (ε22000) 286 (ε23000) 210 (ε24000) 288 (ε     23000) 210 (ε24000) 288 (ε23000) 209 (ε27000)     284 (ε27000) 211 (ε23000) 283 (ε25000) (λ     .sub.max.sup. EtOH, nm) 228 (ε15000) 331 (ε43000) 228     (ε16000) 330 (ε42000) 228 (ε16000) 330 (ε     42000) 226 (ε18000) 327 (ε53000) 227 (ε16000)     327 (ε48000)  272 (ε27000) 273 (ε27000) 273     (ε27000) 269 (ε31000) 270 (ε28000) Mass spectrum     549 607 607 423 439 (SIMS, m/z) [C.sub.30 H.sub.33 N.sub.2 O.sub.8     ].sup.+ [C.sub.32 H.sub.35 N.sub.2 O.sub.10 ].sup.+ [C.sub.33 H.sub.35     N.sub.2 O.sub.10 ].sup.+ [C.sub.24 H.sub.27 N.sub.2 O.sub.5 ].sup.+     [C.sub.24 H.sub.27 N.sub.2 O.sub.6 ].sup.+ Proton NMR 1.56 (3H,d,J=7Hz)     1.86, 2.20 1.86, 2.06, 2.20, 2.24 (each Same as in the left 1.53     (3H,d,J=7Hz) 3.09 (3H,S) 3.10 (3H,S) 3.26 (3H,S) (DMSOd.sub.6, δ     in ppm, 2.25 (each 3H,S) 3.11 (3H,S) 3H,S) 3.13 (3H,S) 4.26 (3H,S)  3.26     (3H,S) 3.71 (1H,m) 3.70 (1H,m) 4.02 (1H,m) CD.sub.2 HSOCD.sub.3 proton     3.30 (3H,S) 4.25 (3H,S) 4.48 (1H,m) 4.61 (2H,m)  4.00 (1H,m) 4.10 (1H,m)     4.23 3.78 (1H,m) 3.96 (1H,m) chemical shift (δ 2.50) 4.53 (1H,m)     4.99 (1H,t) 5.50 5.18 (1H,t) 5.55 (1H,t)  (3H,S) 4.32 (1H,m) 5.38 (1H,d)     4.11 (2H,m) 4.23 (3H,S) was used as internal (1H,t) 5.76 (1H,dd) 6.70     (1H, 5.80 (1H,dd) 6.73 (1H,d  5.46 (1H,d) 5.64 (1H,d) 4.95 (1H,t) 5.45     (1H,d) standard, Intensity of d,J=8Hz,1'-H) 7.24 (1H,dd, J=8Hz,1'-H)     7.24 (1H,dd,J=2,  6.23 (1H,d,J=9Hz,1'-H) 5.51 (1H,d) 5.66 (1H,d) NMR     magnetic field was J=2,9Hz) 7.68 (1H,d,J=9Hz) 9Hz) 7.70 (1H,d,J=9Hz)     7.91  7.22 (1H,dd,J=2,9Hz) 7.64 6.17 (1H,d,J=9Hz,1'-H) indicated in each     7.90 (1H,d,J=2Hz) 8.59 (2H,AB) (1H,d,J=2Hz) 8.59 (2H,S)  (1H,d,J=9Hz)     7.86 (1H,d,J=2Hz) 7.23 (1H,dd,J=2,9Hz) compound) 9.58 (1H,S) 10.13     (1H,S) 9.59 (1H,brs) 10.08 (1H,S)  8.57 (2H,S) 9.52 (1H,S) 7.64 (1H,d,J=9     Hz)  (360 MHz) (270 MHz)  10.07 (1H,S) 360 MHz 7.86 (1H,d,J=2Hz) 8.58     (2H,S)      9.54 (1H,brs) 10.07 (1H,S)      (360 MHz) Elementary     analysis Molecular formula  C.sub.32 H.sub.35 N.sub.2 O.sub.10      Br.2.5H.sub.2 O C.sub.32 H.sub.35 N.sub.2 O.sub.10 Br.2.5H.sub.2 O     C.sub.24 H.sub.27 N.sub.2 O.sub.5 Br C.sub.24 H.sub.27 N.sub.2 O.sub.6     Br.1.5H.sub.2 O Calc. (C, H, N) % -- 52.47, 5.50, 3.82 52.47, 5.50, 3.82     57.26, 5.41, 5.56 52.76, 5.53, 5.13 Found (C, H, N) %  52.43, 5.13, 3.76     52.56, 5.35, 3.91 56.94, 5.40, 5.53 52.50, 5.18, 5.04       Example No. 162 163 164 165 166       R.sup.2      ##STR265##      ##STR266##      ##STR267##      ##STR268##      ##STR269##       R.sup.1 OH OA.sub.C OH OA.sub.C OH   R.sup.3 CH.sub.3 CH.sub.2     CH.sub.3 CH.sub.2      CH.sub.3     ##STR270##      ##STR271##       X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.- Crystalline form     Amorphous orange powder Amorphous orange powder Amorphous orange powder     Amorphous red powder Amorphous reddish orange powder Specific (28°      C.) (27° C.) (28° C.) (28° C.) (28° C.)     rotatory [α].sub.D -78° (C= 0.07, DMSO) +25° (C=     0.11, MeOH) +9° (C= 0.06, DMSO) +33° (C= 0.15, MeOH)     +13° (C= 0.06, DMSO) power Infrared absorption 3250, 2900, 1630,     1585, 1500, 1750, 1630, 1585, 1560, 1470, 3300, 1630, 1585, 1560, 1470,     1750, 1630, 1580, 1470, 1400, 1630, 1580, 1470, 1400, 1280, (KBr,     cm.sup.-1) 1470, 1400, 1220, 1110, 1050 1400, 1370, 1200, 1135, 1050,     1415, 1220, 1050, 800, 735 1370, 1210, 1140, 1055, 940, 1215, 1140,     1100, 1050, 910,   910, 805, 740  910, 810 805, 3300 Ultraviolet     absorption 211 (ε 23000) 283 (ε25000) 209 (ε23000     ) 283 (ε23000) 212 (ε25000) 283 (ε27000) 210     (ε22000) 283 (ε23000) 212 (ε25000) 284 (ε     28000) (λ .sub.max.sup. EtOH, nm) 227 (ε16000) 327     (ε48000) 245 (ε23000) 320 (ε60000) 227 (ε     17000) 327 (ε52000) 245 (ε24000) 320 (ε57000)     230 (ε17000) 328 (ε53000)  270 (ε28000) 258     (ε27000) 270 (ε31000) 258 (ε27000) 270 (ε     31000) Mass spectrum 439 605 437 619 451 (SIMS, m/z) [C.sub.24 H.sub.27     N.sub.2 O.sub.6 ].sup.+ [C.sub.33 H.sub.37 N.sub.2 O.sub.9 ].sup.+     [C.sub.25 H.sub.29 N.sub.2 O.sub.5 ].sup.+ [C.sub.34 H.sub.39 N.sub.2     O.sub.9 ].sup.+ [C.sub.26 H.sub.31 N.sub.2 O.sub.5 ].sup.+ Proton NMR     Same as in the left 1.50 (3H,t,J=7Hz) 1.54 (3H,d 1.45 (3H,t,J=7Hz) 1.53     (3H, 1.54 (3H,d,J=6.5Hz) 1.71 (3H, 1.53 (3H,d,J=7Hz) 1.67 (3H,d,     (DMSOd.sub.6, δ in ppm,  J=7Hz) 1.85, 2.20, 2.24 (each d,J=7Hz)     3.07 (3H,S) 3.70 d,J=6.5Hz) 1.75 (3H,d,J=6.5Hz) J=7Hz) 1.68 (3H,d,J=7Hz)     CD.sub.2 HSOCD.sub.3 proton  3H,S) 2.38 (3H,S) 3.14 (3H,S) (1H,m) 3.99     (1H,m) 4.09 (1H,m) 1.85, 2.19, 2.24 (each 3H,S) 3.04 (3H,S) 3.70 (1H,m)     3.99 chemical shift (δ 2.50)  3.37 (3H,S) 4.53 (1H,m) 4.32 (1H,m)     4.75 (2H,q,J=7Hz) 2.37 (3H,S) 3.07 (3H,S) 4.54 (1H,q) 4.08 (1H,m) 4.31     was used as internal  4.85 (2H,q,J=7Hz) 4.99 (1H,t) 5.37 (1H,d) 5.46     (1H,d) (1H,m) 4.99 (1H,t,J=4Hz) (1H,dq) 5.37 (1H,d,J=7.5Hz) standard,     Intensity of  5.51 (1H,t) 5.79 (1H,dd) 6.71 5.64 (1H,d) 6.23 (1H,d,J=9Hz,      5.50 (1H,t,J=4Hz) 5.62 (1H,dq, 5.46 (1H,d,J=5.5Hz) 5.63 NMR magnetic     field was  (1H,d,J=8Hz,1'-H) 7.56 (1H,dd, 1'-H) 7.23 (1H,dd,J=2,9Hz)     J=6.5Hz) 5.77 (1H,dt,J=2Hz, (1H,d,J=4Hz) 5.52 (1H,dq, indicated in each     J=2,9Hz) 7.94 (1H,d,J=9Hz) 7.69 (1H,d,J=9Hz) 7.89 (1H, 8Hz) 6.71     (1H,d,J=8Hz,1'-H) J=7Hz) 6.24 (1H,d,J=9Hz,1'-H) compound)  8.32 (1H,d,J=2     Hz) 8.70 (2H, d,J=2Hz) 8.58 (1H,d,J=7.5Hz) 7.48 (1H,dd,J=2.5Hz,9Hz) 7.18     (1H,dd,J=2.5Hz,9Hz)   ABq) 10.22 (1H,S) 8.63 (1H,d,J=7.5Hz) 9.54 8.06     (1H,d,J=9Hz) 8.31 (1H,d 7.84 (1H,d,J=9Hz) 7.90 (1H,d,   (360 MHz)     (1H,brs) 10.10 (1H,S) J=2.5Hz) 8.66 (1H,d,J=7.5Hz) J=2.5Hz) 8.59 (2H,S)     9.54    (360 MHz) 8.69 (1H,d,J=7.5Hz) 10.21 (1H,S) 10.11 (1H,S) (360     MHz)     (1H,S) (270 MHz) Elementary analysis Molecular formula C.sub.46     H.sub.39 N.sub.2 O.sub.9 Br.1.5H.sub.2 O  C.sub.24 H.sub.29 N.sub.2     O.sub.4 Br -- -- Calc. (C, H, N) % 63.54, 4.86, 3.22 -- 56.08, 5.84,     5.23 Found (C, H, N) % 63.51, 4.92, 3.25  56.32, 5.43, 5.19       Example No. 167 168 169 170       R.sup.2      ##STR272##      ##STR273##      ##STR274##      ##STR275##       R.sup.1 OA.sub.C OH H H      R.sup.3     ##STR276##      ##STR277##      CH.sub.3 CH.sub.3      X.sup.- Br.sup.- Br.sup.- Br.sup.- Br.sup.- Crystalline form Amorphous     reddish orange powder Amorphous orange powder Amorphous yellowish orange     powder Amorphous yellowish orange powder Specific (28° C.)     (28° C.) +24° (C=0.13,CH.sub.3 OH) -17° (C=0.07,     DMSO) rotatory [α].sub.D +25° (C= 0.13, MeOH) +28°     (C= 0.05, DMSO) Infrared absorption 1750, 1603, 1580, 1560, 1465, 3300,     1630, 1580, 1550, 1480, 1750, 1630, 1590, 1560, 1480, 3300, 1630, 1585,     1560, 1480, (KBr, cm.sup.-1) 1400, 1370, 1300, 1210, 1140, 1410, 1270,     1210, 1050, 920, 1445, 1395, 1365, 1240, 1210 1470, 1450, 1400, 1300,     1240,  1050, 910, 810, 755 800, 740 1050 1050, 800, 750 Ultraviolet     absorption 210 (ε22000) 283 (ε23000) 212 (ε26000)      284 (ε27000) 209 (ε22000) 287 (ε24000) 209     (ε21000) 286 (ε25000) (λ .sub.max.sup. EtOH, nm)     245 (ε24000) 330 (ε59000) 227 (ε17000) 328     (ε53000) 245 (ε22000) 320 (ε60000) 244 (ε     23000) 316 (ε68000)  258 (ε26000) 270 (ε31000)     256 (ε23000) 254 (ε25000) Mass spectrum 631 463 533 407     (SIMS, m/z) [C.sub.35 H.sub.39 N.sub.2 O.sub.9 ].sup.+ [C.sub.27     H.sub.31 N.sub.2 O.sub.5 ].sup.+ [C.sub.30 H.sub.33 N.sub.2 O.sub.7     ].sup.+ [C.sub.24 H.sub.27 N.sub.2 O.sub.4 ].sup.+ Proton NMR 0.46     (4H,m) 1.30 (1H,m) 0.42 (4H,m) 1.25 (1H,m) 1.55 (3H,d,J=7.3Hz) 1.54     (3H,d,J=7.3Hz) 3.16 (3H,S) (DMSOd.sub.6, δ      in ppm, 1.54 (3H,d,J=6.6Hz) 1.53 (3H,d,J=7Hz) 3.12 (3H,S) 1.86, 2.19,     2.24 (each 3H,S) 3.71, 4.00, 4.10, 4.33 (each 1H,m) CD.sub.2 HSOCD.sub.3     proton 1.87, 2.19, 2.24 (each 3H,S) 3.70 (1H,m) 3.99 (1H,m) 3.17, 3.41,     4.32 (each 3H,S) 4.30 (3H,S) 5.39 (1H,d) chemical shift (δ 2.50)     2.37 (3H,S) 3.17 (3H,S) 4.09 (1H,m) 4.32 (1H,m) 4.52 (1H,m) 4.99 (1H,t)     5.47 (1H,d) 5.65 (1H,d) was used as internal 4.52 (1H,m) 4.80 (2H,d,J=6Hz     ) 4.71 (2H,d,J=6Hz) 5.38 (1H,d) 5.51 (1H,t) 5.80 (1H,dd) 6.26 (1H,d,J=9Hz     ,1'-H) standard, Intensity of 5.00 (1H,t) 5.51 (1H,t) 5.46 (1H,d) 5.64     (1H,d) 6.70 (1H,d,J=8.5Hz,1'-H) 7.47 (1H,t,J=7.5Hz) NMR magnetic field     was 5.81 (1H,dd) 6.72 (1H,d, 6.14 (1H,d,J=9Hz,1'-H) 7.51 (1H,t,J=7.5Hz)     7.76 (1H,t,J=7.5Hz) indicated in each J=8Hz,1'-H) 7.53 (1H,dd,J=2, 7.21     (1H,dd,J=2,9Hz) 7.78 (1H,t,J=7.5Hz) 7.84 (1H,d,J=7.5Hz) compound) 9Hz)     7.97 (1H,d,J=9Hz) 8.32 7.72 (1H,d,J=9Hz) 7.89 (1H,d, 7.87 (1H,d,J=7.5Hz)     8.52 (1H,d,J=7.5Hz)  (1H,d,J=2Hz) 8.71 (2H,ABq) J=2Hz) 8.59 (1H,d,J=7.5Hz     ) 8.57 (1H,d,J=7.5Hz) 8.64 (2H,ABq)  10.23 (1H,S) (270 MHz) 8.64     (1H,d,J=7.5Hz) 9.54 8.66 (2H,S) 10.18 (1H,S) 10.15 (1H,S)   (1H,brs)     10.13 (1H,S)   (360 MHz) Elementary analysis Molecular formula  C.sub.27     H.sub.31 N.sub.2 O.sub.5 Br Calc. (C, H, N) % -- 59.67, 5.75, 5.15 -- --     Found (C, H, N) %  59.42, 5.88, 5.10       Example No. 171 172       R.sup.2      ##STR278##      ##STR279##       R.sup.1 OCH.sub.3 OCH.sub.3 R.sup.3 CH.sub.3 CH.sub.3 X.sup.- Br.sup.-     Br.sup.- Crystalline form Amorphous reddish powder Amorphous reddish     orange powder Specific +42° (C= 0.10, CH.sub.3 OH) +20°     (C= 0.04, DMSO) rotatory [α].sub.D power Infrared absorption 1760,     1640, 1590, 1560, 3300, 1630, 1580, 1560, 1470 (KBr, cm.sup.-1) 1480,     1400, 1380, 1300, 1390, 1290, 1250, 1220, 1180  1220, 1140, 1070, 1050     1140, 1105, 1090, 1045 Ultraviolet absorption 211 (ε24000) 285     (ε24000) 210 (ε24000) 282 (ε26000) (λ     .sub.max.sup. EtOH, nm) 229 (ε18000) 328 (ε51000) 228     (ε17000) 325 (ε55000)  270 (ε29000) 268 (.epsilon     .29000) Mass spectrum 563 437 (SIMS, m/z) [C.sub.31 H.sub.35 N.sub. 2     O.sub.8 ].sup.+ [C.sub.25 H.sub.29 N.sub.2 O.sub.5 ].sup.+ Proton NMR     1.54 (3H,d,J=7Hz) 1.54 (3H,d,J=7Hz) 3.13 (3H,S) (DMSOd.sub.6, δ in     ppm, 1.86, 2.19, 2.24 (each 3H,S) 3.30 (3H,S) 3.96 (3H,S) CD.sub.2     HSOCD.sub.3 proton 3.15 (3H,S) 3.40 (3H,S) 4.27 (3H,S) 3.71 (1H,m)     chemical shift (δ 2.50) 3.97 (3H,S) 4.30 (3H,S) 4.00 (1H,m) 4.09     (1H,dt, was used as internal 4.50 (1H,m) 4.99 (1H,t,J=4Hz) J=3,9Hz),     4.32 (1H,dq,J=2,7Hz) standard, Intensity of 5.51 (1H,t,J=4Hz) 5.38     (1H,d,J=7.5Hz) NMR magnetic field was 5.80 (1H,dd,J=4,8Hz) 5.46 (1H,d,J=5     .5Hz) indicated in each 6.67 (1H,d,J=8Hz,1'-H) 5.65 (1H,d,J=4Hz) 6.25     (1H,d, compound) 7.43 (1H,dd,J=2,9Hz) J=9Hz) 7.40 (1H,dd,J=2.5,9Hz)     7.82 (1H,d,J=9Hz) 8.02 (1H, 7.77 (1H,d,J=9Hz) 7.96 (1H,d,  d,J=2Hz) 8.62     (2H,S) J=2.5Hz) 8.59 (1H,d,J=8Hz)  10.14 (1H,S) 8.60 (1H,d,J=8Hz) 10.12     (1H,S) Elementary analysis Molecular formula  C.sub.25 H.sub.29 N.sub.2     O.sub.5 Br.H.sub.2 O Calc. (C, H, N) % -- 56.08, 5.84, 5.23 Found (C, H,     N) %  55.90, 5.61, 5.20

EXAMPLE 113 Preparation of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)-9-acetoxy-6-methylellipticiniumchloride ##STR280##

A 809 mg amount of 2,3,5-tri-O-benzoyl-α-D-xylofuranosyl chloride wasdissolved in 30 ml of nitromethane and, then, 223 mg of9-acetoxy-6-methylellipticine and 220 mg of cadmium carbonate were addedthereto. The mixture was heated under reflux for 10 minutes. Theinsoluble matter was removed by filtration and the filtrate wasconcentrated.

The residue obtained above was subjected to silicagel columnchromatography (Kieselgel 60, 100 ml), followed by eluting withmethylene chloride-methanol (94:6-92:8). Thus, 170 mg of the product wasobtained. This product was then subjected to gel filtration columnchromatography (Sephadex LH20, 4.6 cmφ×32 cm), followed by eluting withmethanol. As a result, 149 mg (27% yield) of the desired compound wasobtained.

The results are shown in Table 2.

Similarly,2-(2,3,5-tri-O-benzoyl-β-L-xylofuranosyl)-9-acetoxy-6-methylellipticiniumchloride was obtained from 2,3,5-tri-O-benzoyl-α-L-xylofuranosylchloride.

EXAMPLES 114 to 119

The following ellipticine derivatives were prepared in the same manneras in Example 113. The results are shown in Table 2.

Example 114:

2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-9-acetoxy-6-methylellipticiniumbromide.

2-(2,3,5-tri-O-benzoyl-β-L-ribofuranosyl)-9-acetoxy-6-methylellipticiniumbromide.

Example 115:

2-(2,3,5-tri-O-benzoyl-α-L-arabinofuranosyl)-9-acetoxy-6-methylellipticiniumbromide.

2-(2,3,5-tri-O-benzoyl-β-D-arabinofuranosyl)-9-acetoxy-6-methylellipticiniumbromide.

Example 116:

2-(2,3-di-O-benzoyl-5-deoxy-α-L-arabinofuranosyl)-9-acetoxy-6-methylellipticiniumchloride.

Example 117:

2-(2,3-di-O-benzoyl-β-D-erythrofuranosyl)-9-acetoxy-6-methylellipticiniumchloride.

2-(2,3-di-O-benzoyl-β-L-erythrofuranosyl)-9-acetoxy-6-methylellipticiniumchloride.

Example 118:

2-(2,3-di-O-benzoyl-5-deoxy-β-D-ribofuranosyl)-9-acetoxy-6-methylellipticiniumchloride.

Example 119:

2-(2,3,5-tri-O-benzyl-β-D-arabinofuranosyl)-9-acetoxy-6-methylellipticiniumbromide.

2-(2,3,5-tri-O-benzyl-β-L-arabinofuranosyl)-9-acetoxy-6-methylellipticiniumbromide.

In Example 119, 1',2'-cis-compound was prepared from2,3,5-tri-O-benzyl-α-D-arabinofuranosyl bromide or2,3,5-tri-O-benzyl-α-L-arabinofuranosyl bromide.

EXAMPLE 120 Preparation of2-β-D-xylofuranosyl-9-hydroxy-6-methylellipticinium chloride ##STR281##

A 126 mg amount of2-(2,3,5-tri-O-benzoyl-β-D-xylofuranosyl)-9-acetoxy-6-methylellipticiniumchloride was dissolved in 38 ml of methanol saturated with gaseousammonia and the mixture was allowed to stand at room temperatureovernight. After concentrating in vacuo, the resultant residue wasdissolved in 10 ml of hot methanol. Ethyl acetate was added to thesolution to cause crystallization. The powder was collected byfiltration and was washed with a solvent mixture of ethyl acetate andmethanol (4:1) .Thus, 63 mg (90% yield) of the desired compound wasobtained.

The results are shown in Table 2.

Similarly, 2-β-L-xylofuranosyl-9-hydroxy-6-methylellipticinium chloridewas obtained.

EXAMPLES 121 to 126

The following ellipticine derivatives were prepared in the same manneras in Example 120. The results are shown in Table 2.

Example 121:

2-β-D-ribofuranosyl-9-hydroxy-6-methylellipticinium bromide.

2-β-L-ribofuranosyl-9-hydroxy-6-methylellipticinium bromide.

Example 122:

2-α-L-arabinofuranosyl-9-hydroxy-6-methylellipticinium bromide.

2-α-D-arabinofuranosyl-9-hydroxy-6-methylellipticinium bromide.

Example 123:

2-(5-deoxy-α-L-arabinofuranosyl)-9-hydroxy-6-methylellipticiniumchloride.

Example 124:

2-β-D-erythrofuranosyl-9-hydroxy-6-methylellipticinium chloride.

2-β-L-erythrofuranosyl-9-hydroxy-6-methylellipticinium chloride.

Example 125:

2-(5-deoxy-β-D-ribofuranosyl)-9-hydroxy-6-methylellipticinium chloride.

The following ellipticine derivatives were prepared in the same manneras in Example 109. The results are shown in Table 2.

Example 126:

2-β-D-arabinofuranosyl-9-hydroxy-6-methylellipticinium bromide.

2-β-L-arabinofuranosyl-9-hydroxy-6-methylellipticinium bromide.

EXAMPLE 127 Preparation of2-(2,3,5-tri-O-benzoyl-D-lyxofuranosyl)-9-acetoxy-6-methylellipticiniumchloride ##STR282##

By using 150 mg of 9-acetoxy-6-methylellipticine and 424 mg of2,3,5-tri-O-benzoyl-D-lyxofuranosyl chloride, 224 mg (60% yield) of thedesired compound was prepared in the same manner as in Example 113.

This compound had two stereoisomers on the 1-position of the sugar at aratio of the α-form/β-form=5/1. The data in Table 2 represent the valuesof the α- and β- form separately in NMR spectrum and the values of themixture in the other items.

EXAMPLE 128

2-(2,3,5-tri-O-benzoyl-L-lyxofuranosyl)-9-acetoxy-6-methylellipticiniumchloride was prepared in the same manner as in Example 127.

This compound also had two stereoisomers at the same ratio of α-/β-formas that of D-enantiomer. The physical data are shown in Table 2 as inExample 127.

EXAMPLE 129 Preparation of2-D-lyxofuranosyl-9-hydroxy-6-methylellipticinium chloride ##STR283##

By using 203 mg of the compound obtained in Example 127, 84 mg (74%yield) of the desired compound was prepared in the same manner as inExample 120. This product was also a mixture of the α-form/β-form=5/1with respect to the 1-position of the sugar.

The NMR data of the α- and β-form are separately shown and the otherdata represent those of the mixture of the α- and β-form in Table 2.

EXAMPLE 130

2-L-lyxofuranosyl-9-hydroxy-6-methylellipticinium chloride having theα-form/the β-form=5/1 was prepared in the same manner as in Example 129.

The results are shown in Table 2 as in Example 129.

EXAMPLE 131 Preparation of2-(2,3,4-tri-O-acetyl-β-L-ribopyranosyl)-9-acetoxy-6-methylellipticiniumbromide ##STR284##

The reaction was carried out by using 100 mg of9-acetoxy-6-methylellipticine, 288 mg of2,3,4-tri-O-acetyl-β-L-ribopyranosyl bromide, 150 mg of cadmiumcarbonate, and 10 ml of nitromethane in the same manner as mentionedabove. As a result, 206 mg of the desired compound was prepared.

The results are shown in Table 2.

EXAMPLE 132

2-(2,3,4-tri-O-acetyl-β-D-ribopyranosyl)-9-acetoxy-6-methylellipticiniumbromide was prepared in the same manner as in Example 131.

The results are shown in Table 2.

EXAMPLE 133 Preparation of2-(2,3,4-tri-O-acetyl-β-L-fucopyranosyl)-9-acetoxy-6-methylellipticiniumbromide ##STR285##

The reaction was carried out by using 100 mg of9-acetoxy-6-methylellipticine, 220 mg of2,3,4-tri-O-acetyl-L-fucopyranosyl bromide, 120 mg of cadmium carbonate,and 10 ml of nitromethane in the same manner as mentioned above. As aresult 176 mg (84% yield) of the desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 134

2-(2,3,4-tri-O-acetyl-β-D-fucopyranosyl)-9-acetoxy-6-methylellipticiniumbromide was prepared in the same manner as in Example 133.

The results are shown in Table 2.

EXAMPLES 135 to 142

The following ellipticine derivatives were prepared in the same manneras in Examples 131 and 133. The results are shown in Table 2.

Example 135:

2-(2,3,4-tri-O-acetyl-β-D-arabinopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

Example 136:

2-(2,3,4-tri-O-acetyl-β-L-arabinopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

Example 137:

2-(2,3,4-tri-O-acetyl-α-D-lyxopyranosyl)-9-acetoxy-6-methylellipticiniumchloride.

Example 138:

2-(2,3,4-tri-O-acetyl-α-L-lyxopyranosyl)-9-acetoxy-6-methylellipticiniumchloride.

Example 139:

2-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

2-(2,3,4,6-tetra-O-acetyl-β-L-galactopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

Example 140:

2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

2-(2,3,4,6-tetra-O-acetyl-β-L-glucopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

Example 141:

2-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)-9-acetoxy-6-methylellipticiniumchloride.

Example 142:

2-(methyl2,3,4-tri-O-acetyl-β-D-glucuronopyranosyl)-9-acetoxy-6-methylellipticiniumbromide.

EXAMPLE 143 Preparation of2-(2,3,4-tri-O-acetyl-D-xylopyranosyl)-9-acetoxy-6-methylellipticiniumbromide ##STR286##

The reaction was carried out by using 100 mg of9-acetoxy-6-methylellipticine, 210 mg of2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide, 120 mg of cadmiumcarbonate, and 10 ml of nitromethane in the same manner as mentionedabove. As a result, 107 mg (52% yield) of the desired compound wasobtained.

This product had a mixture of two isomers of the α- and β-form withrespect to the 1-position of the sugar at a ratio of α-form/β-form=1/3.

The NMR data of the α- and β-form are separately shown and the otherdata represent those of the mixture of the α- and β-form.

EXAMPLE 144

2-(2,3,4-tri-O-acetyl-L-xylopyranosyl)-9-acetoxy-6-methylellipticiniumbromide was prepared in the same manner as in Example 143.

The ratio of α-form/β-form was 1/3.

The physical data are shown in Table 2 as in Example 143.

EXAMPLE 145 Preparation of2-β-L-ribopyranosyl-9-hydroxy-6-methylellipticinium bromide ##STR287##

A 122 mg amount of the compound obtained in Example 131 was dissolved in10 ml of methanol saturated with gaseous ammonia to effect thehydrolysis in the same manner as mentioned above. Thus, 53 mg (59%yield) of the desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 147

2-β-D-ribopyranosyl-9-hydroxy-6-methylellipticinium bromide was preparedin the same manner as in Example 145. The results are shown in Table 2.

EXAMPLE 147 Preparation of2-β-L-fucopyranosyl-9-hydroxy-6-methylellipticinium bromide ##STR288##

The reaction was carried out by using 153 mg of the compound obtained inExample 133 and 15 ml of methanol saturated with gaseous ammonia in thesame manner as mentioned above. Thus, 82 mg (72% yield) of the desiredcompound was obtained.

The results are shown in Table 2.

EXAMPLE 148

2-β-D-fucopyranosyl-9-hydroxy-6-methylellipticinium bromide was preparedin the same manner as in Example 147.

The results are shown in Table 2.

EXAMPLE 149 to 155

The following ellipticine derivatives were prepared in the same manneras in Examples 145 and 147. The results are shown in Table 2.

Example 149:

2-α-D-arabinopyranosyl-9-hydroxy-6-methylellipticinium bromide.

Example 150:

2-α-L-arabinopyranosyl-9-hydroxy-6-methylellipticinium bromide.

Example 151:

2-α-D-lyxopyranosyl-9-hydroxy-6-methylellipticinium chloride.

Example 152:

2-α-L-lyxopyranosyl-9-hydroxy-6-methylellipticinium chloride.

Example 153:

2-β-D-galactopyranosyl-9-hydroxy-6-methylellipticinium bromide.

2-β-L-galactopyranosyl-9-hydroxy-6-methylellipticinium bromide.

Example 154:

2-β-D-glucopyranosyl-9-hydroxy-6-methylellipticinium bromide.

2-β-L-glucopyranosyl-9-hydroxy-6-methylellipticinium bromide.

Example 155:

2-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-9-hydroxy-6-methylellipticiniumchloride.

EXAMPLE 156 Preparation of2-β-D-glucuronamidopyranosyl-9-hydroxy-6-methylellipticinium bromide##STR289##

The compound of Example 142 was dissolved in methanol saturated withgaseous ammonia and the mixture was allowed to stand at a temperature of0° C. to 5° C. for 15 hours in the same manner as mentioned above. Thus,the desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 157 Preparation of2-D-xylopyranosyl-9-hydroxy-6-methylellipticinium bromide ##STR290##

The reaction was carried out by using 84 mg of the compound obtained inExample 143 and 10 ml of methanol saturated with gaseous ammonia in thesame manner as mentioned above. Thus, 41 mg (66% yield) of the desiredcompound having two isomers with respect to the 1-position of the sugarat a ratio of the β-form/the β-form=1/3.

The NMR spectra of the α- and β-form, and the other physical data of themixture are shown in Table 2.

EXAMPLE 158

2-L-xylopyranosyl-9-hydroxy-6-methylellipticinium bromide was preparedin the similar manner as in Example 157. The ratio of the α-form/β-formwas also 1/3.

The NMR spectra of the α- and β-form, and the other properties of themixture are shown in Table 2.

EXAMPLE 159 Preparation of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-hydroxy-6-methylellipticiniumbromide ##STR291##

A 190 mg amount of 9-hydroxy-6-methylellipticine, 190 mg of cadmiumcarbonate, and 399 mg of α-bromoaceto-L-rhamnose were suspended in 19 mlof nitromethane and the suspension was heated under reflux for 10minutes. After removing the insoluble matter, the reaction mixture wasconcentrated. The residue was subjected to column chromatography of 200ml of silicagel (elution: methylene chloride-methanol=95:5-92:8) andSephadex LH20 (4.0 cmφ×23 cm, methanol). Thus, 214 mg (49% yield) of thedesired compound was obtained.

The results are shown in Table 2.

EXAMPLE 160

The following compound was prepared in the same manner as in Example159. The results are shown in Table 2

2-(2,3,4,6-tetra-O-acetyl-β-D-mannopyranosyl)-9-hydroxy-6-methylellipticiniumbromide

2-(2,3,4,6-tetra-O-acetyl-α-L-mannopyranosyl)-9-hydroxy-6-methylellipticiniumbromide

EXAMPLE 161

Preparation of 2-α-L-rhamnopyranosyl-9-hydroxy-6-methylellipticiniumbromide ##STR292##

A 194 mg amount of the compound obtained in Example 159 was dissolved in32 ml of methanol saturated with gaseous ammonia and the solution wasallowed to stand in a refrigerator for 15 hours. Thus, 98 mg (79% yield)of the desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 162

2-α-D-mannopyranosyl-9-hydroxy-6-methylellipticinium bromide and2-α-L-mannopyranosyl-9-hydroxy-6-methylellipticinium bromide wereprepared in the same manner as in Example 161.

The results are shown in Table 2.

EXAMPLE 163 Preparation of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-acetoxy-6-ethylellipticiniumbromide ##STR293##

A 190 mg amount of 9-acetoxy-6-ethylellipticine, 170 mg of cadmiumcarbonate, and 292 mg (1.6 equivalent) of2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl bromide were suspended in 17 mlof nitromethane and was heated under reflux for 10 minutes. Theinsoluble matter was removed by filtration and the filtrate wasconcentrated. The residue thus obtained was subjected to silicagelcolumn chromotography (silicagel 100 ml, elution solvent:methylenechloride:methanol=96:4-93:7) and Sephadex LH20 column chromatography (4cmφ×30 cm, methanol). Thus, 262 mg (75% yield) of the desired compoundwas obtained.

The results are shown in Table 2.

EXAMPLE 164 Preparation of2-α-L-rhamnopyranosyl-9-hydroxy-6-ethylellipticinium bromide ##STR294##

A 240 mg amount of the compound obtained in Example 163 was dissolved in40 ml of methanol saturated with gaseous ammonia and was allowed tostand overnight in a refrigerator. The reaction mixture was concentratedand the resultant residue was powdered with methanolethyl acetate. Thus,131 mg (72% yield) of the desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 165 Preparation of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-acetoxy-6-isopropylellipticiniumbromide ##STR295##

A 142 mg amount of 9-acetoxy-6-isopropylellipticine, 100 mg of cadmiumcarbonate, and 200 mg of 2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl bromidewere suspended in 12 ml of nitromethane and the mixture was heated underreflux for 10 minutes. After removing the insoluble matter byfiltration, the filtrate was concentrated. The resultant residue wassubjected to silicagel column chromatography (silicagel: 80 g, solvent:5% methanol-chloroform) and, then, to Sephadex LH-20 columnchromatography (4.8 cmφ×27.5 cm, methanol). Thus, 152 mg (53% yield) ofthe desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 166 Preparation of2-α-L-rhamnopyranosyl-9-hydroxy-6-isopropylellipticinium bromide##STR296##

A 130 mg amount of the compound obtained in Example 165 was dissolved in10 ml of methanol saturated with ammonia and was allowed to stand for 21hours in a refrigerator. The residue obtained after concentrating waspowdered with methanol-ethyl acetate. Thus, 70 mg (71% yield) of thedesired compound was obtained.

The results are shown in Table 2.

EXAMPLE 167 Preparation of2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-9-acetoxy-6-cyclopropylmethylellipticiniumbromide ##STR297##

A 172 mg amount of 9-acetoxy-6-cyclopropylmethylellipticine, 170 mg ofcadmium carbonate, and 275 mg of 2,3,4-tri-O-acetyl-α-L-rhamnopyranosylbromide were suspended in 17 ml of nitromethane and the mixture washeated under reflux for 7 minutes. After removing the insoluble matterby filtration, the filtrate was concentrated. The residue thus obtainedwas subjected to silicagel column chromatography (gel: 100 ml, solvent:methylene chloride: methanol=95:5) and, then, to Sephadex LH-20 (2.5cmφ×53 cm, methanol). Thus, 259 mg (76% yield) of the desired compoundwas obtained.

The results are shown in Table 2.

EXAMPLE 168 Preparation of2-α-L-rhamnopyranosyl-9-hydroxy-6-cyclopropylmethylellipticinium bromide##STR298##

A 184 mg amount of the compound obtained in Example 167 was dissolved in32 ml of methanol saturated with ammonia and was allowed to standovernight in a refrigerator. After concentrating, the resultant residuewas crystallized from methanol-ethyl acetate. Thus, 122 mg (87% yield)of the desired compound was obtained.

The results are shown in Table 2.

EXAMPLE 169 to 172

The following ellipticine derivatives were prepared in the same manneras mentioned above. The results are shown in Table 2.

Example 169:

2-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-6-methylellipticinium bromide

Example 170:

2-α-L-rhamnopyranosyl-6-methylellipticinium bromide

Example 171:

2-(2,3,4-tri-O-acetyl-αL-rhamnopyranosyl)-9-methoxy-6-methylellipticinium bromide.

Example 172: 2-α-L-rhamnopyranosyl-9-methoxy-6-methylellipticiniumbromide.

REFERENCE EXAMPLE 1 Synthesis of 9-Hydroxy-6-isopropylellipticine

A 1.0 g amount of 9-acetoxyellipticine was dissolved in 40 ml ofanhydrous dimethylformamide and, then, to this solution, 160 ml ofsodium hydride (50% in oil) and 10 ml of anhydrous dimethylformamidewere added at a temperature of 0° C. The mixture was stirred for 30minutes. To this reaction mixture, 0.33 ml of isopropyl iodide was addedat a temperature of 0° C. and the mixture was then stirred at roomtemperature for 43 hours. Ice water was added to the reaction mixtureand the mixture was extracted 4 times with chloroform. After the organiclayer was washed with water, the organic layer was dried over anhydrousmagnesium sulfate. The mixture was concentrated to form the residue. Theresidue thus obtained was subjected to silicagel column chromatographyand eluted with 1% methanol-chloroform solvent. Thus, 268 mg (24% yield)of 9-acetoxy-6-isopropylellipticine was obtained.

The compound thus obtained was treated with methanol saturated withammonia at a temperature of 0° C. to 5° C. for 15 hours to obtain thedesired compound at a yield of 22%. The physical data is as follows:

Crystalline form: prism crystal (yellowish brown)

Melting point: 270°-285° C. (sublimation with decomposition).

IR spectrum (KBr, cm⁻¹): 1600, 1590, 1580, 1500, 1465, 1390, 1380, 1370,1280, 1270, 1260, 1210, 1170, 1145, 1135, 1125, 1100, 1025.

UV spectrum (λ_(max) ^(C).sbsp.2^(H).sbsp.5^(OH), nm): 212(ε26,000),250(ε30,000) 277(ε40,000), 298(ε55,000).

Mass spectrum (EI, m/z): 304(M⁺), 288, 261, 247, 233, 217, 77, 28.

NMR spectrum (DMSO-d₆, δppm): 1.57(6H, d, J=7 Hz), 2.91(3H, s) 3.18(3H,s), 5.27(1H, dq, J=7 Hz), 7.01(1H, dd, J=2.5, 8.5 Hz), 7.62(1H, d, J=8.5Hz), 7.79(1H, d, J=2.5 Hz), 7.94(1H, d, J=6.5 Hz), 8.42(1H, d, J=6.5Hz), 9.19(1H, s), 9.65(1H, s). Elementary analysis (C₂₀ H₂₀ N₂ O)

    ______________________________________                                               C(%)        H(%)    N(%)                                               ______________________________________                                        Calc.:   78.92         6.62    9.20                                           Found:   78.80         6.42    9.10                                           ______________________________________                                    

REFERENCE EXAMPLE 2 Synthesis of9-Acetoxy-6-Cyclopropylmethylellipticine

A 1.0 g amount of 9-acetoxyellipticine was dissolved in 40 ml ofanhydrous dimethylformamide and, then, to this solution, 131 mg ofsodium hydride was added. The mixture was stirred at room temperaturefor 10 minutes. To this reaction mixture, a solution of 442 mg ofbromomethylcyclopropane in 1 ml of anhydrous dimethylformamide wasadded. The mixture was then stirred at room temperature for 6 hours.Water was added to the reaction mixture to form the precipitated powder.After the powder was separated by filtration and was subjected tosilicagel column chromatography (gel: 200 ml, 1% methanol-chloroform).Thus, 577 mg (49% yield) of the desired compound was obtained.

Crystalline form: Yellow needle-like crystal.

Melting point: 200°-205° C.

IR spectrum (KBr, cm⁻¹): 3000, 2920, 1740, 1595, 1480, 1370, 1300, 1220,1200, 1140, 1010.

UV spectrum (λ_(max) ^(C).sbsp.2^(H).sbsp.5^(OH), nm): 205(ε16,000),220(ε16,000), 250(ε23,000), 278(ε38,000), 290(ε53,000), 298(ε60,000).

Mass spectrum (EI, m/z): 358M⁺), 316, 232, 204.

NMR spectrum (DMSO-d₆, δppm): 0.33-0.47(4H, m), 1.22(1H, m), 2.34(3H,s), 3.04(3H, s), 3.19(3H, s), 4.62(2H, d, J=6 Hz), 7.34(1H, dd, J=2, 9Hz), 7.71(1H, d, J=9 Hz), 8.04(1H, d, J=6.5 Hz), 8.11(1H, d, J=2 Hz),8.46(1H, d, J=6.5 Hz), 9.71(1H, s).

    ______________________________________                                        Elementary analysis (C.sub.23 H.sub.22 N.sub.2 O.sub.2)                              C(%)        H(%)    N(%)                                               ______________________________________                                        Calc.:   77.07         6.19    7.82                                           Found:   77.05         6.21    7.89                                           ______________________________________                                    

EVALUATION TEST

The antineoplastic or antitumor activity of the various ellipticinederivatives listed in Table 3 prepared above was evaluated, by usingmouse experimental tumor L-1210, as follows:

(i) Animal used:

BDF₁ mouse, female, 6 weeks ago, average body weight of 17 to 18 g, 6mice in one group

(ii) Type of tumor used:

L 1210 (mouse lymphoid leukemia cells ) 10⁵ cells/mouse,intraperitoneally injection (ip)

(iii) Sample administration method:

L 1210 was intraperitoneally injected into mice and the sample wassuccessively administered once a day for 5 days from the second dayafter the injection of L 1210 cells.

(iv) Evaluation method:

The effectivity of the sample was determined in increased life span ofmean survival day of the adminstered group (ILS%) when compared with thecontrol group. ##EQU1##

The results were shown in Table 3. From the results shown in Table 3, itis clear that the present ellipticine derivatives have excellent orremarkable antineoplastic or antitumor effects against mouse lymphoidleukemia L 1210. Thus, it is believed that the present ellipticinederivatives are effective as an antitumor agent. ##STR299##

                  TABLE 3                                                         ______________________________________                                        Results of Screening Test (L 1210)                                                          Dose     Tox-           80 days'                                Example No. (R.sup.2)                                                                       (mg/kg)  icity  ILS %   survival                                ______________________________________                                        Control       0        0/6    0       0/6                                     2             20       0/6    33.8    0/6                                     D-galactopyranosyl                                                                          40       0/6    39.0    0/6                                                   80       6/6    toxic   0/6                                     4             10       0/6    57.8    0/6                                     D-ribofuranosyl                                                                             20       0/6    80.0    0/6                                     12            10       0/6    28.9    0/6                                     L-rhamnopyranosyl                                                                           20       0/6    37.8    0/6                                                   40       0/6    40.0    0/6                                     18            5        0/6    53.3    0/6                                     D-ribofuranosyl                                                                             10       0/6    60.0    0/6                                                   30       0/6    75.6    0/6                                     26            5        0/6    44.4    0/6                                     L-rhamnopyranosyl                                                                           10       0/6    62.5    0/6                                     53            10       0/6    53.3    0/6                                     L-rhamnopyranosyl                                                                           30       0/6    68.8    0/6                                                   60       0/6    88.8    0/6                                     62            5        0/6    62.2    0/6                                     D-galactopyranosyl                                                                          10       0/6    86.7    0/6                                                   20       0/6    >728.9  4/6                                                   40       6/6    toxic   0/6                                     63            5        0/6    >209.6  1/6                                     L-arabinofuranosyl                                                                          10       0/6    >378.7  2/6                                                   30       6/6    toxic   0/6                                     64            2.5      0/6    56.8    0/6                                     D-arabinofuranosyl                                                                          5        0/6    61.4    0/6                                                   10       0/6    72.7    0/6                                                   20       0/6    90.9    0/6                                     66            5        0/6    56.8    0/6                                     D-mannopyranosyl                                                                            10       0/6    87.7    0/6                                                   30       6/6    toxic   0/6                                     66            5        0/6    >361.7  2/6                                     L-mannopyranosyl                                                                            10       0/6    >243.6  1/6                                                   30       0/6    4.3     0/6                                     67            5        0/6    95.7    0/6                                     D-talopyranosyl                                                                             10       0/6    >211.3  1/6                                                   30       6/6    toxic   0/6                                     68            0.1      0/6    6.7     0/6                                     L-galactopyranosyl                                                                          0.5      0/6    28.6    0/6                                                   2.5      0/6    57.1    0/6                                                   5        4/6    toxic   0/6                                     69            5        0/6    97.8    0/6                                     D-allopyranosyl                                                                             10       0/6    >254.4  2/6                                                   30       2/6    toxic   0/6                                     70            5        0/6    58.4    0/6                                     L-glucopyranosyl                                                                            10       0/6    14.3    0/6                                                   30       6/6    toxic   0/6                                     71            5        0/6    68.9    0/6                                     L-rhamnopyranosyl                                                                           10       0/6    95.6    0/6                                                   30       0/6    >693.3  4/6                                     72            5        0/6    78.1    0/6                                     2-deoxy-D-    10       0/6    >390.4  2/6                                     ribofuranosyl 20       0/6    >200.0  1/6                                     73            5        0/6    46.7    0/6                                     5-deoxy-      10       0/6    80.0    0/6                                     D-ribofuranosyl                                                                             30       0/6    >230.0  1/6                                     74            5        0/6    82.2    0/6                                     5-deoxy-L-    10       0/6    73.3    0/6                                     arabinofuranosyl                                                                            30       0/6    >261.1  1/6                                     75            5        0/6    54.4    0/6                                     D-fucopyranosyl                                                                             10       0/6    68.9    0/6                                                   30       0/6    124.4   0/6                                     76            5        0/6    62.2    0/6                                     L-fucopyranosyl                                                                             10       0/6    117.8   0/6                                                   30       0/6    >583.3  3/6                                     77            5        0/6    117.8   0/6                                     D-xylofuranosyl                                                                             10       0/6    >384.4  2/6                                                   30       0/6    >682.2  4/6                                     77            5        0/6    97.8    0/6                                     L-xylofuranosyl                                                                             10       0/6    >227.8  1/6                                                   30       0/6    >386.7  2/6                                     79            5        0/6    122.2   0/6                                     D-erythrofuranosyl                                                                          10       0/6    4.7     0/6                                                   30       0/6    toxic   0/6                                     80            5        0/6    87.0    0/6                                     L-ribopyranosyl                                                                             10       0/6    >512.0  3/6                                                   30       0/6    >943.5  6/6                                     81            5        0/6    57.5    0/6                                     D-ribopyranosyl                                                                             10       0/6    75.3    0/6                                                   30       0/6    112.3   0/6                                     82            5        0/6    106.7   0/6                                     L-ribofuranosyl                                                                             10       0/6    >391.1  2/6                                                   30       0/6    2.2     0/6                                     83            5        0/6    86.7    0/6                                     D-ribofuranosyl                                                                             10       0/6    137.8   0/6                                                   30       0/6    toxic   0/6                                     84            2.5      0/6    77.3    0/6                                     D-arabinopyranosyl                                                                          5        0/6    93.2    0/6                                                   10       0/6    >381.8  2/6                                                   20       0/6    >605.7  3/6                                     85            5        0/6    76.4    0/6                                     L-arabinopyranosyl                                                                          10       0/6    115.3   0/6                                                   30       0/6    >839.4  5/6                                     86            5        0/6    >191.0  1/6                                     D-lyxofuranosyl                                                                             10       0/6    >675.6  4/6                                                   30       0/6    >966.7  6/6                                     87            5        0/6    >234.4  1/6                                     L-lyxofuranosyl                                                                             10       0/6    >552.2  3/6                                                   30       0/6    --      0/6                                     88            5        0/6    83.3    0/6                                     L-lyxopyranosyl                                                                             10       0/6    >213.8  1/6                                                   30       0/6    >786.2  5/6                                     89            5        0/6    121.8   0/6                                     D-lyxopyranosyl                                                                             10       0/6    >651.1  4/6                                                   30       6/6    toxic   0/6                                     90            5        0/6    6.5     0/6                                     2-acetamido-2-                                                                              10       0/6    19.5    0/6                                     deoxy-D-glucopyranosyl                                                                      30       0/6    39.0    0/6                                     92            5        0/6    48.9    0/6                                     D-glucuronamido-                                                                            10       5/6    toxic   0/6                                     pyranosyl     30       6/6    toxic   0/6                                     93            5        0/6    77.8    0/6                                     D-xylopyranosyl                                                                             10       0/6    >248.6  1/6                                                   30       0/6    >805.3  5/6                                     94            5        0/6    >385.1  2/6                                     L-xylopyranosyl                                                                             10       0/6    >395.7  2/6                                                   30       6/6    toxic   0/6                                     95            5        0/6    81.2    0/6                                     L-rhamnopyranosyl                                                                           10       0/6    127.3   0/6                                                   30       0/6    >614.8  3/6                                     96            5        0/6    71.2    0/6                                     β-D-arabinofuranosyl                                                                   10       0/6    80.8    0/6                                                   30       0/6    >261.6  1/6                                     96            5        0/6    64.4    0/6                                     β-L-arabinofuranosyl                                                                   10       0/6    >239.7  1/6                                                   30       0/6    >268.5  1/6                                     97            5        0/6    72.2    0/6                                     5-deoxy-β-L-arabino-                                                                   10       0/6    >216.7  1/6                                     furanosyl     30       0/6    >216.7  1/6                                     112           5        0/6    35.9    0/6                                     D-glucopyranosyl                                                                            10       0/6    52.4    0/6                                                   30       4/6    toxic   0/6                                     120           5        0/6    75.6    0/6                                     D-xylofuranosyl                                                                             10       0/6    86.7    0/6                                                   30       0/6    >554.4  3/6                                     121           5        0/6    74.0    0/6                                     D-ribofuranosyl                                                                             10       0/6    101.4   0/6                                                   20       0/6    308.2   1/6                                     122           5        0/6    65.8    0/6                                     L-arabinofuranosyl                                                                          10       0/6    270.7   1/6                                                   30       0/6    644.0   3/6                                     123           5        0/6    69.3    0/6                                     5-deoxy-L-arabino-                                                                          10       0/6    66.7    0/6                                     furanosyl     30       0/6    80.0    0/6                                     124           5        0/6    61.4    0/6                                     D-erythrofuranosyl                                                                          10       0/6    84.1    0/6                                                   30       0/6    4.5     0/6                                     129           5        0/6    76.7    0/6                                     D-lyxofuranosyl                                                                             10       0/6    84.9    0/6                                                   30       0/6    >300.0  1/6                                     145           5        0/6    54.8    0/6                                     L-ribopyranosyl                                                                             10       0/6    57.5    0/6                                                   30       0/6    >265.3  1/6                                     147           5        0/6    59.1    0/6                                     L-fucopyranosyl                                                                             10       0/6    >235.2  1/6                                                   30       0/6    >420.5  2/6                                     149           5        0/6    108.9   0/6                                     D-arabinopyranosyl                                                                          10       0/6    >576.7  3/6                                                   30       5/6    toxic   0/6                                     150           5        0/6    62.2    0/6                                     L-arabinopyranosyl                                                                          10       0/6    113.3   0/6                                                   30       0/6    >314.4  1/6                                     151           5        0/6    74.0    0/6                                     D-lyxopyranosyl                                                                             10       0/6    76.7    0/6                                                   30       0/6    17.4    0/6                                     152           5        0/6    93.2    0/6                                     L-lyxopyranosyl                                                                             10       0/6    115.1   0/6                                                   30       0/6    >501.4  2/6                                     153           5        0/6    33.3    0/6                                     D-galactopyranosyl                                                                          10       0/6    66.7    0/6                                                   30       6/6    toxic   0/6                                     154           5        0/6    46.7    0/6                                     D-glucopyranosyl                                                                            10       0/6    80.0    0/6                                                   30       4/6    toxic   0/6                                     156           5        0/6    31.1    0/6                                     D-glucuronamido-                                                                            10       0/6    48.9    0/6                                     pyranosyl     30       5/6    toxic   0/6                                     157           5        0/6    112.5   0/6                                     D-xylopyranosyl                                                                             10       0/6    97.7    0/6                                                   30       0/6    >848.9  5/6                                     161           5        0/6    75.5    0/6                                     L-rhamnopyranosyl                                                                           10       0/6    126.7   0/6                                                   30       0/6    >500.0  2/6                                     162           5        0/6    67.7    0/6                                     D-mannopyranosyl                                                                            10       0/6    84.5    0/6                                                   30       6/6    toxic   0/6                                     164           5        0/6    32.0    0/6                                     L-rhamnopyranosyl                                                                           10       0/6    53.7    0/6                                                   30       0/6    64.0    0/6                                     Ellipticine   120      0/6    127.5   0/6                                     9-Methoxyellipticine                                                                        30       0/6    27.3    0/6                                     9-Hydroxyellipticine                                                                        60       0/6    78.6    0/6                                     Celiptium     5        0/6    47.8    0/6                                     Adriamycin    0.25     0/6    84.8    0/6                                     ______________________________________                                    

We claim:
 1. A ellipticine derivative having the formula: ##STR300##wherein R¹ represents a hydrogen atom, a hydroxyl group, an alkoxylgroup having 1 to 4 carbon atoms, or an acyloxy group having 2 to 7carbon atoms;R² represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, analdohexuronic acid residue, an acylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated deoxyaldose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated N-acylaminoaldose residue having an amino group substitutedwith an acyl group with 2 to 4 carbon atoms and having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic acid residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic acid ester residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an arylalkylated aldose residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms, an arylalkylated deoxyaldose residue having, substitutedfor the hydrogen atom of the hydroxyl group of the sugar, an alkylacylgroup with 7 to 8 carbon atoms, an arylalkylated N-acylaminoaldoseresidue having an amino group with an acyl group with 2 to 4 carbonatoms and having, substituted for the hydrogen of the hydroxyl group ofthe sugar, an arylalkyl group with 7 to 8 carbon atoms, an arylalkylatedaldohexuronic amide residue having, substituted for the hydrogen atom ofthe hydroxyl group of the sugar, an arylalkyl group with 7 to 8 carbonatoms, an arylalkylated aldohexuronic acid residue having, substitutedfor the hydrogen atom of the hydroxyl group of the sugar, an arylalkylgroup with 7 to 8 carbon atoms, or an arylalkylated aldohexuronic acidester residue having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an arylalkyl group with 7 to 8 carbon atoms; and R³represents a hydrogen atom, a linear, branched, cyclic, or cyclic-linearalkyl group having 1 to 5 carbon atoms; X.sup.⊖ represents apharmaceutically acceptable inorganic or organic acid anion; and thebond represented by N.sup.⊕ --R² in the formula (I) represents aglycoside bond between a nitrogen atom in the 2-position of theellipticine and a carbon atom in the 1-position of the sugar.
 2. Anellipticine derivative as claimed in claim 1, wherein R² in the generalformula (I) represents an aldotetrose residue, an acylated aldotetroseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, or an arylalkylated aldotetrose residuehaving an arylalkyl group with 7 to 8 carbon atoms substituted for thehydrogen atom of the hydroxyl group of the sugar.
 3. An ellipticinederivative as claimed in claim 1, wherein R² in the formula (I)represents an aldopentose residue, an acylated aldopentose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, or an arylalkylated aldopentose residue havingan arylalkyl group with 7 to 8 carbon atoms substituted for the hydrogenatom of the hydroxyl group of the sugar.
 4. An ellipticine derivative asclaimed in claim 1, R² in the formula (I) represents an aldohexoseresidue, an acylated aldohexose residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,or an arylalkylated aldohexose residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms.
 5. An ellipticine derivative as claimed inclaim 1, wherein R² in the formula (I) represents a 2-deoyaldopentoseresidue, an acylated 2-deoxyaldopentose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, with an alkylacylgroup with 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbonatoms, or an arylalkylated 2-deoxyaldopentose residue having anarylalkyl group with 7 to 8 carbon atoms substituted for the hydrogenatom of the hydroxyl group of the sugar.
 6. An ellipticine derivative asclaimed in claim 1, wherein R² in the formula (I) represents a2-deoxyaldohexose residue, an acylated 2-deoxyaldohexose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atom, or an arylalkylated 2-deoxyaldohexose residue having anarylalkyl group with 7 to 8 carbon atoms substituted for the hydrogenatom of the hydroxyl group of the sugar.
 7. An ellipticine derivative asclaimed in claim 1, wherein R² is the formula (I) represents a5-deoxyaldopentose residue, an acylated 5-deoxyaldopentose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, or an arylalkylated 5-deoxyaldopentose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms.
 8. An ellipticinederivative as claimed in claim 1, wherein R² is the formula (I)represents a 6-deoxyaldohexose residue, an acylated 6-deoxyaldohexoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, or an arylalkylated 6-deoxyaldohexoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms.
 9. Anellipticine derivative as claimed in claim 1, wherein R² is the formula(I) represents an N-acylaminoaldohexose residue having an amino groupsubstituted with an acyl group with 2 to 4 carbon atoms, an acylatedN-acylaminoaldohexose residue having an amino group substituted with anacyl group with 2 to 4 carbon atoms and having, substituted for thehydrogen atom or the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,or an arylalkylated N-acylaminoaldohexose residue having an acyl groupsubstituted with an amino group with 2 to 4 carbon atoms having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms.
 10. An ellipticine derivativeas claimed in claim 1, wherein R² in the formula (I) represents analdohexuronic acid residue, an aldohexuronic amide residue, an acylatedaldohexuronic amide residue having, substituted for the hydrogen atom ofthe hydroxyl group of the sugar, an alkyacyl group with 2 to 4 carbonatoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedaldohexuronic acid residue having, substituted for the hydrogen atom ofthe hydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbonatoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedaldohexuronic acid-lower alkyl ester residue having, substituted for thehydrogen atom of the hydroyl group of the sugar, an alkylacyl group with2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms, anarylalkylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic acid residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedaldohexuronic acid-lower alkyl ester residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms.
 11. An ellipticine derivative as claimed inclaim 1, wherein X.sup.⊖ in the formula (I) is an anion derived from aninorganic acid selected from the group consisting of hydrochloric acid,sulfuric acid, phosphoric acid, hydroidic acid, hydrobromic acid, andperchloric acid or an anion derived from an organic acid selected fromthe group consisting of acetic acid, propionic acid, oxalic acid,tartaric acid, lactic acid, malic acid, formic acid, fumaric acid,maleic acid, butyric acid, valeric acid, caproic acid, heptanoic acid,and capric acid.
 12. An ellipticine derivative as claimed in claim 1,wherein R³ in the formula (I) represents a methyl group, an ethyl group,a propyl group, an isopropyl group, a butyl group, an isobutyl group, asec-butyl group, a pentyl group, a cyclopropylmethyl group, or acyclopropylethyl group.
 13. A process for producing an ellipticinederivative having the formula (Ia): ##STR301## wherein R¹ represents ahydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 4 carbonatoms, or an acyloxy group having 2 to 7 carbon atoms;R³ represents ahydrogen atom, a linear, branched, cyclic, or cyclic-linear alkyl grouphaving 1 to 5 carbon atoms; R⁴ represents an acylated aldose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated deoxyaldose residue having,substituted for the hydrogen atom or the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated N-acylaminoaldose residue having an aminogroup substituted with an acyl group with 2 to 4 carbon atoms andhaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic amide residuehaving, substituted for the hydrogen atom or the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic acid ester residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an arylalkylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated N-acylaminoaldose residue having an amino group with anacyl group with 2 to 4 carbon atoms and having, substituted for thehydrogen atom or the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedaldohexuronic acid ester residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; Y represents a halogen atom; and the bond represented byN⁺ --R⁴ in the formula (Ia) represents a glycoside bond between anitrogen atom in the 2-position of the ellipticine and a carbon atom inthe 1-position of the sugar, or the formula (Ib): ##STR302## wherein R¹,R³, and R⁴ are the same as defined above and Z.sup.⊖ is apharmaceutically acceptable inorganic or organic acid anion; whichcomprises reacting a compound having the formula (II): ##STR303##wherein R¹ and R³ are the same as defined above with an aldosederivative having the formula (III):

    R.sup.4 --Y                                                (III)

wherein R⁴ and Y are the same as defined above; in the presence orabsence of an acid captured reagent in an organic solvent to form anellipticine derivative having the formula (Ia), which may be optionallysubjected to an ion-exchange reaction with an ion-exchange resin to forman ellipticine derivative having the formula (Ib).
 14. A process forproducing an ellipticine derivative having the formula (Ic): ##STR304##wherein R³ represents a hydrogen atom, a linear, branched, cyclic, orcyclic-linear alkyl group having 1 to 5 carbon atoms;R⁵ represents ahydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbonatoms; R⁶ represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, analdohexuronic acid residue, an arylalkylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic acid residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedN-acrylaminaldose residue having an amino group substituted with an acylgroup with 2 to 4 carbon atoms and having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; and Z.sup.⊖ is a pharmaceutically acceptable inorganic ororganic acid anion, which comprises hydrolyzing the ellipticinederivative having the formula (Ib): ##STR305## wherein R³ and Z.sup.⊖are as defined above, R¹ represents a hydrogen atom, a hydroxyl group,an alkoxyl group having 1 to 4 carbon atoms, or an acyloxy group having2 to 7 carbon atoms; and R⁴ represents an acylated aldose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated deoxyaldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated N-acylaminoaldose residue having an aminogroup substituted with an acyl group with 2 to 4 carbon atoms andhaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic acid ester residuehaving substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an arylalkylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylated deoxyaldoseresidue having substituted for the hydrogen atom or the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated N-acylaminoaldose residue having an amino group with anacyl group with 2 to 4 carbon atoms and having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic amide residuehaving substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedaldohexuronic acid ester residue having substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; in the presence of a base to form the ellipticinederivative having the formula (Ic).
 15. A process for producing anellipticine derivtive having the formula (Id): ##STR306## wherein R³represents a hydrogen atom, a linear, branched, cyclic, or cyclic-linearalkyl group having 1 to 5 carbon atoms;R⁵ represents a hydrogen atom, ahydroxyl group, or an alkoxyl group having 1 to 4 carbon atoms; and R⁶represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, analdohexuronic acid residue, an arylalkylated aldose residue having,substituted for the hydrogen atom or the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylted aldohexuronic acid residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedN-acylaminoaldose residue having an amino group substituted with an acylgroup with 2 to 4 carbon atoms and having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; and Y represents a halogen atom, which compriseshydrolyzing the ellipticine derivative having the formula (Ia):##STR307## wherein R³ and Y.sup.⊖ are as defined above, R¹ represents ahydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 4 carbonatoms, or an acyloxy group having 2 to 7 carbon atoms; and R⁴ representsan acylated aldose residue having, substituted for the hydrogen atom ofthe hydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbonatoms or an arylacyl group with 7 to 9 carbon atoms, an acylateddeoxyaldose residue having, substituted for the hydrogen atom of thehydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbon atomsor an arylacyl group with 7 to 9 carbon atoms, an acylatedN-acylaminoaldose residue having an amino group substituted with an acylgroup with 2 to 4 carbon atoms and having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an alkylacyl group with 2 to 4carbon atoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedaldohexuronic amide residue having, substituted for the hydrogen atom ofthe hydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbonatoms or an arylacyl group with 7 to 9 carbon atoms, an acylatedaldohexuronic acid ester residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an alkylacyl group with 2 to 4carbon atoms or an arylacyl group with 7 to 9 carbon atoms, anarylalkylated aldose residue having, substituted for the hydrogen atomor the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms, an arylalkylated deoxyaldose residue having, substitutedfor the hydrogen atom of the hydroxyl group of the sugar, an arylalkylgroup with 7 to 8 carbon atoms, an arylalkylated N-acylaminoaldoseresidue having an amino group with an acyl group with 2 to 4 carbonatoms and having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, or an arylalkylated aldohexuronic acid esterresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms; and the bondrepresented by N⁺ --R⁴ in the formula (Ia) represents a glycoside bondbetween a nitrogen atom in the 2-position of the ellipticine and acarbon atom in the 1-position of the sugar, in the presence of a base toform an ellipticine derivative (Id).
 16. A process for producing anellipticine derivative having the formula (Ig): ##STR308## wherein R³represents a hydrogen atom, a linear, branched, cyclic, or cyclic-linearalkyl group having 1 to 5 carbon atoms;R⁷ represents a hydrogen atom, ahydroxyl group, or an acyloxy group having 2 to 7 carbon atoms, and R⁸represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, analdohexuronic acid residue, an acylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated deoxyaldose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic acid residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,or an acylated N-acylaminoaldose residue having an amino groupsubstituted with an acyl group with 2 to 4 carbon atoms and having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms; and Y represents a halogen atom; which comprisestreating the ellipticine derivative having the formula (Ia): ##STR309##wherein R³ and Y.sup.⊖ are as defined above, R¹ represents a hydrogenatom, a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, oran acyloxy group having 2 to 7 carbon atoms; and R⁴ represents anacylated aldose residue having, substituted for the hydrogen atom of thehydroxyl group of the sugar, an alkylacyl group with 2 to 4 carbon atomsor an arylacyl group with 7 to 9 carbon atoms, an acylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, an acylated N-acylaminoaldose residuehaving an amino group substituted with an acyl group with 2 to 4 carbonatoms and having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an alkylacyl group with 2 to 4 carbon atoms or anarylacyl group with 7 to 9 carbon atoms, an acylated aldohexuronic amideresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, an acylated aldohexuronic acid esterresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, an arylalkylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated N-acylaminoaldose residue having an amino group with anacyl group with 2 to 4 carbon atoms and having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedaldohexuronic acid ester residue having, substituted for the hydrogenatom of the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; and the bond represented by N⁺ --R⁴ in the formula (Ia)represents a glycoside bond between a nitrogen atom in the 2-position ofthe elliptiine and a carbon atom in the 1-position of the sugar; with atrialkyl silyl iodide to form the ellipticine derivative having theformula (Ig).
 17. A process for producing an ellipticine derivativehaving the formula (Ih): ##STR310## wherein R³ represents a hydrogenatom, a linear, branched, cyclic, or cyclic-linear alkyl group having 1to 5 carbon atoms;R⁹ represents a hydrogen atom or a hydroxyl group, R¹⁰represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, or analdohexuronic acid residue, and Y.sup.⊖ represents a halogen atom; whichcomprises hydrolyzing the ellipticine derivative (Ig): ##STR311##wherein R³ and Y is as defined above; R⁷ represents a hydrogen atom, ahydroxyl group, or an acyloxy group having 2 to 7 carbon atoms, and R⁸represents an aldose residue, a deoxyaldose residue, anN-acylaminoaldose residue having a substituted acyl group with 2 to 4carbon atoms bonded to the N atom, an aldohexuronic amide residue, analdohexuronic acid residue, an acylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated deoxyaldose residue having, substituted forthe hydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic amide residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,an acylated aldohexuronic acid residue having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an alkylacyl groupwith 2 to 4 carbon atoms or an arylacyl group with 7 to 9 carbon atoms,or an acylated N-acylaminoaldose residue having an amino groupsubstituted with an acyl group with 2 to 4 carbon atoms and having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, in the presence of a base to form a ellipticinederivative having the formula (Ih).
 18. A process for producing anellipticine derivative having the formula (If): ##STR312## wherein R³represents a hydrogen atom, a linear, branched, cyclic, or cyclic-linearalkyl group having 1 to 5 carbon atoms;R⁹ represents a hydrogen atom ora hydroxyl group, R¹⁰ represents an aldose residue, a deoxyaldoseresidue, an N-acylaminoaldose residue having a substituted acyl groupwith 2 to 4 carbon atoms bonded to the N atom, an aldohexuronic amideresidue, or an aldohexuronic acid residue, and Z.sup.δ represents ahalogen atom; which comprises ion-exchanging the ellipticine derivativehaving the formula (Ih): ##STR313## wherein R³, R⁹ and R¹⁰ are asdefined above, and Y represents a halogen atom; with an ion-exchangeresin to form the ellipticine derivative having the formula (If).
 19. Aprocess for producing an ellipticine derivative having the formula (Ie):##STR314## wherein R³ represents a hydrogen atom, a linear, branched,cyclic, or cyclic-linear alkyl group having 1 to 5 carbon atoms;R⁷represents a hydrogen atom, a hydroxyl group, or an acyloxy group having2 to 7 carbon atoms, and R⁸ represents an aldose residue, a deoxyaldoseresidue, an N-acylaminoaldose residue having a substituted acyl groupwith 2 to 4 carbon atoms bonded to the N atom, an aldohexuronic amideresidue, an aldohexuronic acid residue, an acylated aldose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated deoxyaldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated aldohexuronic amide residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylted aldohexuronic acid residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, or an acylated N-acylaminoaldose residue having an aminogroup substituted with an acyl group with 2 to 4 carbon atoms andhaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, and Z.sup.⊖ is a pharmaceutically acceptableinorganic or organic acid anion which comprises hydroxylizing theellipticine derivative having the formula (Ib): ##STR315## wherein R³and Z.sup.⊖ are as defined above; R¹ represents a hydrogen atom, ahydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or anacyloxy group having 2 to 7 carbon atoms; and R⁴ represents an acylatedaldose residue having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an alkylacyl group with 2 to 4 carbon atoms or anacryacyl group with 7 to 9 carbon atoms, an acylted deoxyaldose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated N-acylaminoaldose residue havingan amino group substituted with an acyl group with 2 to 4 carbon atomsand having, substituted for the hydrogen atom of the hydroxyl group ofthe sugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacylgroup with 7 to 9 carbon atoms, an acylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic acid ester residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an arylalkylated aldose residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, anarylalkyl group with 7 to 8 carbon atoms, an arylalkylated deoxyaldoseresidue having, substituted for the hydrogen atom of the hydroxyl groupof the sugar, an arylalkyl group with 7 to 8 carbon atoms, anarylalkylated N-acylaminoaldose residue having an amino group with anacyl group with 2 to 4 carbon atoms and having, substituted for thehydrogen atom of the hydroxyl group of the sugar, an arylalkyl groupwith 7 to 8 carbon atoms, an arylalkylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an arylalkyl group with 7 to 8 carbon atoms, or an arylalkylatedaldohexuronic acid ester residue having, substituted for the hydrogenatom or the hydroxyl group of the sugar, an arylalkyl group with 7 to 8carbon atoms; with a trialkyl silyl iodide to form the ellipticinederivative having the formula (Ie).
 20. A process for producing anellipticine derivative having the formula (If): ##STR316## wherein R³represents a hydrogen atom, a linear, branched, cyclic, or cyclic-linearalkyl group having 1 to 5 carbon atoms;R⁹ represents a hydrogen atom ora hydroxyl group, R¹⁰ represents an aldose residue, a deoxyaldoseresidue, an N-acylaminoaldose residue having a substituted acyl groupwith 2 to 4 carbon atoms bonded to the N atom, an aldohexuronic amideresidue, or an aldohexuronic acid residue, and Z.sup.⊖ represents ahalogen atom; which comprises hydroxylicin the ellipticine derivativehaving the formula (Ie): ##STR317## wherein R³ and Z.sup.⊖ are asdefined above; R⁷ represents a hydrogen atom, a hydroxyl group, or anacyloxy group having 2 to 7 carbon atoms, and R⁸ represents an aldoseresidue, a deoxyaldose residue, an N-acylaminoaldose residue having asubstituted acyl group with 2 to 4 carbon atoms bonded to the N atom, analdohexuronic amide residue, an aldohexuronic acid residue, an acylatedaldose residue having, substituted for the hydrogen atom of the hydroxylgroup of the sugar, an alkylacyl group with 2 to 4 carbon atoms or anarylacyl group with 7 to 9 carbon atoms, an acylated deoxyaldose residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic amide residuehaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, an acylated aldohexuronic acid residue having,substituted for the hydrogen atom of the hydroxyl group of the sugar, analkylacyl group with 2 to 4 carbon atoms or an arylacyl group with 7 to9 carbon atoms, an acylated N-acylaminoaldose residue having an aminogroup substituted with an acyl group with 2 to 4 carbon atoms andhaving, substituted for the hydrogen atom of the hydroxyl group of thesugar, an alkylacyl group with 2 to 4 carbon atoms or an arylacyl groupwith 7 to 9 carbon atoms, in the presence of a base to form theellipticine derivative having the formula (If).